Continuous methods for treating liquids and manufacturing certain constituents (e.g., nanoparticles) in liquids, apparatuses and nanoparticles and nanoparticle/liquid solution(s) resulting therefrom

ABSTRACT

Methods and devices for the continuous manufacture of nanop∈rticles, microparticles and nanoparticle/liquid solution(s) are disclosed. The nanoparticles (and/or micron-sized particles) comprise a variety of possible compositions, sizes and shapes. The particles (e.g., nanoparticles) are caused to be present (e. g., created) in a liquid (e.g., water) by utilizing at least one adjustable plasma (e.g., created by at least one AC and/or DC power source), which plasma communicates with at least a portion of a surface of the liquid. The continuous process causes at least one liquid to flow into, through and out of at least one trough member, such liquid being processed, conditioned and/or effected in said trough member(s).

The present application is a U.S. national phase entry of InternationalApplication No. PCT/US2008/008558 which was filed on Jul. 11, 2008. Thatinternational application claims priority to US 60/949,175 filed on Jul.11, 2007, as well as to US 60/649,312, filed on Jul. 12, 2007. All threeof the aforementioned applications are hereby expressly incorporated byreference.

FIELD OF THE INVENTION

This invention relates generally to novel methods and novel devices forthe continuous manufacture of nanoparticles, microparticles andnanoparticle/liquid solution(s). The nanoparticles (and/or micron-sizedparticles) comprise a variety of possible compositions, sizes andshapes. The particles (e.g., nanoparticles) are caused to be present(e.g., created) in a liquid (e.g., water) by, for example, preferablyutilizing at least one adjustable plasma (e.g., created by at least oneAC and/or DC power source), which plasma communicates with at least aportion of a surface of the liquid. At least one subsequent and/orsubstantially simultaneous adjustable electrochemical processingtechnique is also preferred. Multiple adjustable plasmas and/oradjustable electrochemical processing techniques are preferred. Thecontinuous process causes at least one liquid to flow into, through andout of at least one trough member, such liquid being processed,conditioned and/or effected in said trough member(s). Results includeconstituents formed in the liquid including micron-sized particlesand/or nanoparticles (e.g., metallic-based nanoparticles) of novel size,shape, composition and properties present in a liquid.

BACKGROUND OF THE INVENTION

Many techniques exist for the production of nanoparticles includingtechniques set forth in “Recent Advances in the Liquid-Phase Synthesesof Inorganic Nanoparticles” written by Brian L. Cushing, Vladimire L.Kolesnichenko and Charles J. O'Connor; and published in ChemicalReviews, volume 104, pages 3893-3946 in 2004 by the American ChemicalSociety; the subject matter of which is herein expressly incorporated byreference.

Further, the article “Chemistry and Properties of Nanocrystals ofDifferent Shapes” written by Clemens Burda, Xiaobo Chen, Radha Narayananand Mostafa A. El-Sayed; and published in Chemical Reviews, volume 105,pages 1025-1102 in 2005 by the American Chemical Society; disclosesadditional processing techniques, the subject matter of which is hereinexpressly incorporated by reference.

The article “Shape Control of Silver Nanoparticles” written by BenjaminWiley, Yugang Sun, Brian Mayers and Younan Xia; and published inChemistry—A European Journal, volume

Still further, U.S. Pat. No. 7,033,415, issued on Apr. 25, 2006 toMirkin et al., entitled Methods of Controlling Nanoparticle Growth; andU.S. Pat. No. 7,135,055, issued on Nov. 14, 2006, to Mirkin et al.,entitled Non-Alloying Core Shell Nanoparticles; both disclose additionaltechniques for the growth of nanoparticles; the subject matter of bothare herein expressly incorporated by reference.

Moreover, U.S. Pat. No. 7,135,054, which issued on Nov. 14, 2006 to Jinet al., and entitled Nanoprisms and Method of Making Them; is alsoherein expressly incorporated by reference.

The present invention has been developed to overcome a variety ofdeficiencies/inefficiencies present in known processing techniques andto achieve a new and controllable process for making nanoparticles of avariety of shapes and sizes and/or new nanoparticle/liquid materials notbefore achievable.

SUMMARY OF THE INVENTION

This invention relates generally to novel methods and novel devices forthe continuous manufacture of a variety of constituents in a liquidincluding micron-sized particles, nanoparticles andnanoparticle/liquid(s) solution(s). The nanoparticles produced cancomprise a variety of possible compositions, sizes and shapes, whichexhibit a variety of novel and interesting physical, catalytic,biocatalytic and/or biophysical properties. The liquid(s) used andcreated/modified during the process play an important role in themanufacturing of, and/or the functioning of the micron-sized particlesand the nanoparticles. The particles (e.g., nanoparticles) are caused tobe present (e.g., created) in at least one liquid (e.g., water) by, forexample, preferably utilizing at least one adjustable plasma (e.g.,created by at least one AC and/or DC power source), which adjustableplasma communicates with at least a portion of a surface of the liquid.Metal-based electrodes of various composition(s) and/or uniqueconfigurations are preferred for use in the formation of the adjustableplasma(s), but non-metallic-based electrodes can also be utilized.Utilization of at least one subsequent and/or substantially simultaneousadjustable electrochemical processing technique is also preferred.Metal-based electrodes of various composition(s) and/or uniqueconfigurations are preferred for use in the electrochemical processingtechnique(s). Electric fields, magnetic fields, electromagnetic fields,electrochemistry, pH, etc., are just some of the variables that can bepositively effected by the adjustable plasma(s) and/or adjustableelectrochemical processing technique(s). Multiple adjustable plasmasand/or adjustable electrochemical techniques are preferred to achievemany of the processing advantages of the present invention, as well asmany of the novel compositions which result from practicing theteachings of the preferred embodiments. The overall process is acontinuous process, having many attendant benefits, wherein at least oneliquid, for example water, flows into, through and out of at least onetrough member and such liquid is processed, conditioned, modified and/oreffected by said at least one adjustable plasma and/or said at least oneadjustable electrochemical technique. The results of the continuousprocessing include new constituents in the liquid, micron-sizedparticles, nanoparticles (e.g., metallic-based nanoparticles) of novelsize, shape, composition and/or properties suspended in a liquid, suchnanoparticle/liquid mixture being produced in an efficient andeconomical manner.

The phrase “trough member” is used throughout the text. This phraseshould be understood as meaning a large variety of fluid handlingdevices including, pipes, half pipes, channels or grooves existing inmaterials or objects, conduits, ducts, tubes, chutes, hoses and/orspouts, so long as such are compatible with the process disclosedherein.

Additional processing techniques such as applying certain crystal growthtechniques disclosed in copending patent application entitled Methodsfor Controlling Crystal Growth, Crystallization, Structures and Phasesin Materials and Systems; which was filed on Mar. 21, 2003, and waspublished by the World Intellectual Property Organization underpublication number WO 03/089692 on Oct. 30, 2003 and the U.S. NationalPhase application, which was filed on Jun. 6, 2005, and was published bythe United States Patent and Trademark Office under publication number20060037177 on Feb. 23, 2006 (the inventors of each being Bentley J.Blum, Juliana H. J. Brooks and Mark G. Mortenson). The subject matter ofboth applications is herein expressly incorporated by reference. Theseapplications teach, for example, how to grow preferentially one or morespecific crystals or crystal shapes from solution. Further, drying,concentrating and/or freeze drying can also be utilized to remove atleast a portion of, or substantially all of, the suspending liquid,resulting in, for example, dehydrated nanoparticles.

An important aspect of one embodiment of the invention involves thecreation of an adjustable plasma, which adjustable plasma is locatedbetween at least one electrode positioned adjacent to (e.g., above) atleast a portion of the surface of a liquid and at least a portion of thesurface of the liquid itself. The liquid is placed into electricalcommunication with at least one second electrode (or a plurality ofsecond electrodes) causing the surface of the liquid to function as anelectrode helping to form the adjustable plasma. This configuration hascertain characteristics similar to a dielectric barrier dischargeconfiguration, except that the surface of the liquid is an activeelectrode participant in this configuration.

Each adjustable plasma utilized can be located between the at least oneelectrode located above a surface of the liquid and a surface of theliquid due to at least one electrically conductive electrode beinglocated somewhere within (e.g., at least partially within) the liquid.At least one power source (in a preferred embodiment, at least onesource of volts and amps such as a transformer) is connectedelectrically between the at least one electrode located above thesurface of the liquid and the at least one electrode contacting thesurface of the liquid (e.g., located at least partially, orsubstantially completely, within the liquid). The electrode(s) may be ofany suitable composition and suitable physical configuration (e.g., sizeand shape) which results in the creation of a desirable plasma betweenthe electrode(s) located above the surface of the liquid and at least aportion of the surface of the liquid itself.

The applied power (e.g., voltage and amperage) between the electrode(s)(e.g., including the surface of the liquid functioning as at least oneelectrode for forming the plasma) can be generated by any suitablesource (e.g., voltage from a transformer) including both AC and DCsources and variants and combinations thereof. Generally, the electrodeor electrode combination located within (e.g., at least partially belowthe surface of the liquid) takes part in the creation of a plasma byproviding voltage and current to the liquid or solution, however, theadjustable plasma is actually located between at least a portion of theelectrode(s) located above the surface of the liquid (e.g., at a tip orpoint thereof) and one or more portions or areas of the liquid surfaceitself. In this regard, the adjustable plasma can be created between theaforementioned electrodes (i.e., those located above at least a portionof the surface of the liquid and a portion of the liquid surface itself)when a breakdown voltage of the gas or vapor around and/or between theelectrode(s) and the surface of the liquid is achieved or maintained.

In one preferred embodiment of the invention, the liquid compriseswater, and the gas between the surface of the water and the electrode(s)above the surface of the water (i.e., that gas or atmosphere that takespart in the formation of the adjustable plasma) comprises air. The aircan be controlled to contain various different water content(s) or adesired humidity which can result in different compositions, sizesand/or shapes of nanoparticles being produced according to the presentinvention (e.g., different amounts of certain constituents in theadjustable plasma and/or in the solution can be a function of the watercontent in the air located above the surface of the liquid) as well asdifferent processing times, etc.

The breakdown electric field at standard pressures and temperatures fordry air is about 3 MV/m or about 30 kV/cm. Thus, when the local electricfield around, for example, a metallic point exceeds about 30 kV/cm, aplasma can be generated in dry air. Equation (1) gives the empiricalrelationship between the breakdown electric field “E_(c)” and thedistance “d” (in meters) between two electrodes:

$\begin{matrix}{E_{c} = {3000 + {\frac{1.35}{d}{kV}\text{/}m}}} & {{Equation}\mspace{14mu} 1}\end{matrix}$Of course, the breakdown electric field “E_(c)” will vary as a functionof the properties and composition of the gas located between electrodes.In this regard, in one preferred embodiment where water is the liquid,significant amounts of water vapor can be inherently present in the airbetween the “electrodes” (i.e., between the at least one electrodelocated above the surface of the water and the water surface itselfwhich is functioning as one electrode for plasma formation) and suchwater vapor should have an effect on at least the breakdown electricfield required to create a plasma therebetween. Further, a higherconcentration of water vapor can be caused to be present locally in andaround the created plasma due to the interaction of the adjustableplasma with the surface of the water. The amount of “humidity” presentin and around the created plasma can be controlled or adjusted by avariety of techniques discussed in greater detail later herein.Likewise, certain components present in any liquid can form at least aportion of the constituents forming the adjustable plasma locatedbetween the surface of the liquid and the electrode(s) located adjacent(e.g., along) the surface of the liquid. The constituents in theadjustable plasma, as well as the physical properties of the plasma perse, can have a dramatic influence on the liquid, as well as on certainof the processing techniques (discussed in greater detail later herein).

The electric field strengths created at and near the electrodes aretypically at a maximum at a surface of an electrode and typicallydecrease with increasing distance therefrom. In cases involving thecreation of an adjustable plasma between a surface of the liquid and theat least one electrode(s) located adjacent to (e.g., above) the liquid,a portion of the volume of gas between the electrode(s) located above asurface of a liquid and at least a portion of the liquid surface itselfcan contain a sufficient breakdown electric field to create theadjustable plasma. These created electric fields can influence, forexample, behavior of the adjustable plasma, behavior of the liquid,behavior of constituents in the liquid, etc.

In this regard, FIG. 1 a shows one embodiment of a point sourceelectrode 1 having a triangular cross-sectional shape located a distance“x” above the surface 2 of a liquid 3 flowing, for example, in thedirection “F”. An adjustable plasma 4 can be generated between the tipor point 9 of the electrode 1 and the surface 2 of the liquid 3 when anappropriate power source 10 is connected between the point sourceelectrode 1 and the electrode 5, which electrode 5 communicates with theliquid 3 (e.g., is at least partially below the surface 2 of the liquid3). It should be noted that under certain conditions the tip 9′ of theelectrode 5 may actually be located physically slightly above the bulksurface 2 of the liquid 3, but the liquid still communicates with theelectrode through a phenomenon known as “Taylor cones”. Taylor cones arediscussed in U.S. Pat. No. 5,478,533, issued on Dec. 26, 1995 toInculet, entitled Method and Apparatus for Ozone. Generation andTreatment of Water, the subject matter of which is herein expresslyincorporated by reference. In this regard, FIG. 1 b shows an electrode,configuration similar to that shown in FIG. 1 a, except that a Taylorcone “T” is utilized for electrical connection between the electrode 5and the surface 2 (or actually the effective surface 2′) of the liquid3. The creation and use of Taylor cones is discussed in greater detailelsewhere herein.

The adjustable plasma region 4, created in the embodiment shown in FIG.1 a can typically have a shape corresponding to a cone-like structurefor at least a portion of the process, and in some embodiments of theinvention, can maintain such cone-like shape for substantially all ofthe process. The volume, intensity, constituents (e.g., composition),activity, precise locations, etc., of the adjustable plasma(s) 4 willvary depending on a number of factors including, but not limited to, thedistance “x”, the physical and/or chemical composition of the electrode1, the shape of the electrode 1, the power source 10 (e.g., DC, AC,rectified AC, the applied polarity of DC and/or rectified AC, RF, etc.),the power applied by the power source (e.g., the volts applied, the ampsapplied, electron velocity, etc.) the frequency and/or magnitude of theelectric and/or magnetic fields created by the power source applied orambient, electric, magnetic or electromagnetic fields, acoustic fields,the composition of the naturally occurring or supplied gas or atmosphere(e.g., air, nitrogen, helium, oxygen, ozone, reducing atmospheres, etc.)between and/or around the electrode 1 and the surface 2 of the liquid 3,temperature, pressure, volume, flow rate of the liquid 3 in thedirection “F”, spectral characteristics, composition of the liquid 3,conductivity of the liquid 3, cross-sectional area (e.g., volume) of theliquid near and around the electrodes 1 and 5, (e.g., the amount of timethe liquid 3 is permitted to interact with the adjustable plasma 4 andthe intensity of such interactions), the presence of atmosphere flow(e.g., air flow) at or near the surface 2 of the liquid 3 (e.g., fan(s)or atmospheric movement means provided) etc., (discussed in more detaillater herein).

The composition of the electrode(s) 1 involved in the creation of theadjustable plasma(s) 4 of FIG. 1 a, in one preferred embodiment of theinvention, are metal-based compositions (e.g., metals such as platinum,gold, silver, zinc, copper, titanium, and/or alloys or mixtures thereof,etc.), but the electrodes 1 and 5 may be made out of any suitablematerial compatible with the various aspects (e.g., processingparameters) of the inventions disclosed herein. In this regard, whilethe creation of a plasma 4 in, for example, air above the surface 2 of aliquid 3 (e.g., water) will, typically, produce at least some ozone, aswell as amounts of nitrogen oxide and other components (discussed ingreater detail elsewhere herein). These produced components can becontrolled and may be helpful or harmful to the formation and/orperformance of the resultant nanoparticles and/or nanoparticle/solutionsproduced and may need to be controlled by a variety of differenttechniques, discussed in more detail later herein. Further, the emissionspectrum of each plasma 4 is also a function of similar factors(discussed in greater detail later herein). As shown in FIG. 1 a, theadjustable plasma 4 actually contacts the surface 2 of the liquid 3. Inthis embodiment of the invention, material (e.g., metal) from theelectrode 1 may comprise a portion of the adjustable plasma 4 (e.g., andthus be part of the emission spectrum of the plasma) and may be caused,for example, to be “sputtered” onto and/or into the liquid 3 (e.g.,water). Accordingly, when metal(s) are used as the electrode(s) 1,elementary metal(s), metal ions, Lewis acids, Bronsted-Lowry acids,metal oxides, metal nitrides, metal hydrides, metal hydrates and/ormetal carbides, etc., can be found in the liquid 3 (e.g., for at least aportion of the process), depending upon the particular set of operatingconditions associated with the adjustable plasma 4. Such constituentsmay be transiently present or may be semi-permanent or permanent.Further, depending on, for example, electric, magnetic and/orelectromagnetic field strength in and around the liquid 3 and the volumeof liquid 3 (discussed in greater detail elsewhere herein), the physicaland chemical construction of the electrode(s) 1 and 5, atmosphere(naturally occurring or supplied), liquid composition, greater or lesseramounts of electrode(s) materials(s) (e.g., metal(s) or derivatives ofmetals) may be found in the liquid 3. In certain situations, thematerial(s) (e.g., metal(s) or metal(s) composite(s)) or constituents(e.g., Lewis acids, Bronsted-Lowry acids, etc.) found in the liquid 3,or in the plasma 4, may have very desirable effects, in which caserelatively large amounts of such materials will be desirable; whereas inother cases, certain materials found in the liquid 3 (e.g., by-products)may have undesirable effects, and thus minimal amounts of such materialsmay be desired in the liquid-based final product. Accordingly, electrodecomposition can play an important role in the material that is formedaccording to the embodiments disclosed herein. The interplay betweenthese components of the invention are discussed in greater detail laterherein.

Still further, the electrode(s) 1 and 5 may be of similar chemicalcomposition and/or mechanical configuration or completely differentcompositions in order to achieve various compositions and/or structuresof liquids and/or specific effects discussed later herein.

The distance between the electrode(s) 1 and 5; or 1 and 1 (shown laterherein) or 5 and 5 (shown later herein) is one important aspect of theinvention. In general, the location of the smallest distance “y” betweenthe closest portions of the electrode(s) used in the present inventionshould be greater than the distance “x” in order to prevent anundesirable arc or formation of an unwanted corona or plasma occurringbetween the electrode (e.g., the electrode(s) 1 and the electrode(s) 5).Features of the invention relating to electrode design, electrodelocation and electrode interactions between a variety of electrodes arediscussed in greater detail later herein.

The power applied through the power source 10 may be any suitable powerwhich creates a desirable adjustable plasma 4 under all of the processconditions of the present invention. In one preferred mode of theinvention, an alternating current from a step-up transformer (discussedin greater detail later herein) is utilized. In another preferredembodiment, a rectified AC source creates a positively charged electrode1 and a negatively charged surface 2 of the liquid 3. In anotherpreferred embodiment, a rectified AC source creates a negatively chargedelectrode 1 and a positively charged surface 2 of the liquid 3. Further,other power sources such as RF power sources are also useable with thepresent invention. In general, the combination of electrode(s)components 1 and 5, physical size and shape of the electrode(s) 1 and 5,electrode manufacturing process, mass of electrodes 1 and/or 5, thedistance “x” between the tip 9 of electrode 1 above the surface 2 of theliquid 3, the composition of the gas between the electrode tip 9 and thesurface 2, the flow rate and/or flow direction “F” of the liquid 3, theamount of liquid 3 provided, type of power source 10, all contribute tothe design, and thus power requirements (e.g., breakdown electric field)required to obtain a controlled or adjustable plasma 4 between thesurface 2 of the liquid 3 and the electrode tip 9.

In further reference to the configurations shown in FIG. 1 a, electrodeholders 6 a and 6 b are capable of being lowered and raised by anysuitable means (and thus the electrodes are capable of being lowered andraised). For example, the electrode holders 6 a and 6 b are capable ofbeing lowered and raised in and through an insulating member 8 (shown incross-section). The mechanical embodiment shown here include male/femalescrew threads. The portions 6 a and 6 b can be covered by, for example,additional electrical insulating portions 7 a and 7 b. The electricalinsulating portions 7 a and 7 b can be any suitable material (e.g.,plastic, polycarbonate, poly(methyl methacrylate), polystyrene,acrylics, polyvinylchloride (PVC), nylon, rubber, fibrous materials,etc.) which prevent undesirable currents, voltage, arcing, etc., thatcould occur when an individual interfaces with the electrode holders 6 aand 6 b (e.g., attempts to adjust the height of the electrodes).Likewise, the insulating member 8 can be made of any suitable materialwhich prevents undesirable electrical events (e.g., arcing, melting,etc.) from occurring, as well as any material which is structurally andenvironmentally suitable for practicing the present invention. Typicalmaterials include structural plastics such as polycarbonates, plexiglass(poly(methyl methacrylate), polystyrene, acrylics, and the like.Additional suitable materials for use with the present invention arediscussed in greater detail elsewhere herein.

FIG. 1 c shows another embodiment for raising and lowering theelectrodes 1, 5. In this embodiment, electrical insulating portions 7 aand 7 b of each electrode are held in place by a pressure fit existingbetween the friction mechanism 13 a, 13 b and 13 c, and the portions 7 aand 7 b. The friction mechanism 13 a, 13 b and 13 c could be made of,for example, spring steel, flexible rubber, etc., so long as sufficientcontact is maintained therebetween.

Preferred techniques for automatically raising and/or lowering theelectrodes 1, 5 are discussed later herein. The power source 10 can beconnected in any convenient electrical manner to the electrodes 1 and 5.For example, wires 11 a and 11 b can be located within at least aportion of the electrode holders 6 a, 6 b (and/or electrical insulatingportions 7 a, 7 b) with a primary goal being achieving electricalconnections between the portions 11 a, 11 b and thus the electrodes 1,5.

FIG. 2 a shows another schematic of a preferred embodiment of theinvention, wherein an inventive control device 20 is connected to theelectrodes 1 and 5, such that the control device 20 remotely (e.g., uponcommand from another device) raises and/or lowers the electrodes 1, 5relative to the surface 2 of the liquid 3. The inventive control device20 is discussed in more detail later herein. In this one preferredaspect of the invention, the electrodes 1 and 5 can be, for example,remotely lowered and controlled, and can also be monitored andcontrolled by a suitable controller or computer (not shown in FIG. 2 a)containing a software program (discussed in detail later herein). Inthis regard, FIG. 2 b shows an electrode configuration similar to thatshown in FIG. 2 a, except that a Taylor Cone “T” is utilized forelectrical connection between the electrode 5 and the surface 2 (oreffective surface 2′) of the liquid 3. Accordingly, the embodimentsshown in FIGS. 1 a, 1 b and 1 c should be considered to be a manuallycontrolled apparatus for use with the techniques of the presentinvention, whereas the embodiments shown in FIGS. 2 a and 2 b should beconsidered to include an automatic apparatus or assembly which canremotely raise and lower the electrodes 1 and 5 in response toappropriate commands. Further, the FIG. 2 a and FIG. 2 b preferredembodiments of the invention can also employ computer monitoring andcomputer control of the distance “x” of the tips 9 of the electrodes 1(and tips 9′ of the electrodes 5) away from the surface 2 (discussed ingreater detail later herein). Thus, the appropriate commands for raisingand/or lowering the electrodes 1 and 5 can come from an individualoperator and/or a suitable control device such as a controller or acomputer (not shown in FIG. 2 a).

FIG. 3 a corresponds in large part to FIGS. 2 a and 2 b, however, FIGS.3 b, 3 c and 3 d show various alternative electrode configurations thatcan be utilized in connection with certain preferred embodiments of theinvention. FIG. 3 b shows essentially a mirror image electrode assemblyfrom that electrode assembly shown in FIG. 3 a. In particular, as shownin FIG. 3 b, with regard to the direction “F” corresponding to the flowdirection of the liquid 3, the electrode 5 is the first electrode whichcommunicates with the fluid 3 when flowing in the longitudinal direction“F” and contact with the plasma 4 created at the electrode 1 follows.FIG. 3 c shows two electrodes 5 a and 5 b located within the fluid 3.This particular electrode configuration corresponds to another preferredembodiment of the invention. In particular, as discussed in greaterdetail herein, the electrode configuration shown in FIG. 3 c can be usedalone, or in combination with, for example, the electrode configurationsshown in FIGS. 3 a and 3 b. Similarly, a fourth possible electrodeconfiguration is shown in FIG. 3 d. In this FIG. 3 d, no electrode(s) 5are shown, but rather only electrodes 1 a and 1 b are shown. In thiscase, two adjustable plasmas 4 a and 4 b are present between theelectrode tips 9 a and 9 b and the surface 2 of the liquid 3. Thedistances “xa” and “xb” can be about the same or can be substantiallydifferent, as long as each distance “xa” and “xb” does not exceed themaximum distance for which a plasma 4 can be formed between theelectrodes 9 a/9 b and the surface 2 of the liquid 3. As discussedabove, the electrode configuration shown in FIG. 3 d can be used alone,or in combination with one or more of the electrode configurations shownin FIGS. 3 a, 3 b and 3 c. The desirability of utilizing particularelectrode configurations in combination with each other with regard tothe fluid flow direction “F” is discussed in greater detail laterherein.

Likewise, a set of manually controllable electrode configurations,corresponding generally to FIG. 1 a, are shown in FIGS. 4 a, 4 b, 4 cand 4 d, all of which are shown in a partial cross-sectional view.Specifically, FIG. 4 a corresponds to FIG. 1 a. Moreover, FIG. 4 bcorresponds in electrode configuration to the electrode configurationshown in FIG. 3 b; FIG. 4 c corresponds to FIG. 3 c and FIG. 4 dcorresponds to FIG. 3 d. In essence, the manual electrode configurationsshown in FIGS. 4 a-4 d can functionally result in similar materialsproduced according to certain inventive aspects of the invention asthose materials produced corresponding to remotely adjustable (e.g.,remote-controlled by computer or controller means) electrodeconfigurations shown in FIGS. 3 a-3 d. The desirability of utilizingvarious electrode configuration combinations is discussed in greaterdetail later herein.

FIGS. 5 a-5 e show perspective views of various desirable electrodeconfigurations for the electrode 1 shown in FIGS. 1-4 (as well as inother Figures and embodiments discussed later herein). The electrodeconfigurations shown in FIGS. 5 a-5 e are representative of a number ofdifferent configurations that are useful in various embodiments of thepresent invention. Criteria for appropriate electrode selection for theelectrode 1 include, but are not limited to the following conditions:the need for a very well defined tip or point 9, composition, mechanicallimitations, the ability to make shapes from the material comprising theelectrode 1, convenience, the constituents introduced into the plasma 4,the influence upon the liquid 3, etc. In this regard, a small mass ofmaterial comprising the electrodes 1 shown in, for example, FIGS. 1-4may, upon creation of the adjustable plasmas 4 according to the presentinvention (discussed in greater detail later herein), rise to operatingtemperatures where the size and or shape of the electrode(s) 1 can beadversely affected. In this regard, for example, if the electrode 1 wasof relatively small mass (e.g., if the electrode(s) 1 was made of silverand weighed about 0.5 gram or less) and included a very fine point, thenit is possible that under certain sets of conditions that a fine point(e.g., a thin wire having a diameter of only a few millimeters andexposed to a few hundred to a few thousand volts; or a triangular-shapedpiece of metal) would be incapable of functioning as the electrode 1,absent some type of additional interactions (e.g., a cooling means suchas a fan, etc.). Accordingly, the composition of (e.g., the materialcomprising) the electrode(s) 1 may affect possible suitable electrodephysical shape due to, for example, melting points, pressuresensitivities, environmental reactions (e.g., the local environment ofthe adjustable plasma 4 could cause chemical, mechanical and/orelectrochemical erosion of the electrode(s)), etc.

Moreover, it should be understood that in alternative preferredembodiments of the invention, well defined sharp points are not alwaysrequired. In this regard, the electrode 1 shown in FIG. 5 e comprises arounded point. It should be noted that partially rounded or arc-shapedelectrodes can also function as the electrode 1 because the adjustableplasma 4, which is created in the inventive embodiments shown herein(see, for example, FIGS. 1-4), can be created from rounded electrodes orelectrodes with sharper or more pointed features. During the practice ofthe inventive techniques of the present invention, such adjustableplasmas can be positioned or can be located along various points of theelectrode 1 shown in FIG. 5 e. In this regard, FIG. 6 shows a variety ofpoints “a-g” which correspond to initiating points 9 for the plasmas 4a-4-g which occur between the electrode 1 and the surface 2 of theliquid 3. Accordingly, it should be understood that a variety of sizesand shapes corresponding to electrode 1 can be utilized in accordancewith the teachings of the present invention. Still further, it should benoted that the tips 9, 9′ of the electrodes 1 and 5, respectively, shownin various Figures herein, may be shown as a relatively sharp point or arelatively blunt end. Unless specific aspects of these electrode tipsare discussed in greater contextual detail, the actual shape of theelectrode tip(s) shown in the Figures should not be given greatsignificance.

FIG. 7 a shows a cross-sectional perspective view of the electrodeconfiguration corresponding to that shown in FIG. 2 a (and FIG. 3 a)contained within a trough member 30.

This trough member 30 has a liquid 3 supplied into it from the back sideidentified as 31 of FIG. 7 a and the flow direction “F” is out of thepage toward the reader and toward the cross-sectioned area identified as32. The trough member 30 is shown here as a unitary piece of onematerial, but could be made from a plurality of materials fittedtogether and, for example, fixed (e.g., glued, mechanically attached,etc.) by any acceptable means for attaching materials to each other.Further, the trough member 30 shown here is of a rectangular or squarecross-sectional shape, but may comprise a variety of differentcross-sectional shapes (discussed in greater detail later herein).Accordingly, the flow direction of the fluid 3 is out of the page towardthe reader and the liquid 3 flows past each of the electrodes 1 and 5,which are, in this embodiment, located substantially in line with eachother relative to the longitudinal flow direction “F” of the fluid 3within the trough member 30. This causes the liquid 3 to firstexperience an adjustable plasma interaction with the adjustable plasma 4(e.g., a conditioning reaction) and subsequently then the conditionedfluid 3 is permitted to interact with the electrode 5. Specificdesirable aspects of these electrode/liquid interactions and electrodeplacement(s) are discussed in greater detail elsewhere herein.

FIG. 7 b shows a cross-sectional perspective view of the electrodeconfiguration shown in FIG. 2 a (as well as in FIG. 3 a), however, theseelectrodes 1 and 5 are rotated on the page 90 degrees relative to theelectrodes 1 and 5 shown in FIGS. 2 a and 3 a. In this embodiment of theinvention, the liquid 3 contacts the adjustable plasma 4 generatedbetween the electrode 1 and the surface 2 of the liquid 3, and theelectrode 5 at substantially the same point along the longitudinal flowdirection “F” (i.e., out of the page) of the trough member 30. Thedirection of liquid 3 flow is longitudinally along the trough member 30and is out of the paper toward the reader, as in FIG. 7 a. Variousdesirable aspects of this electrode configuration are discussed ingreater detail later herein.

FIG. 8 a shows a cross-sectional perspective view of the same embodimentshown in FIG. 7 a. In this embodiment, as in FIG. 7 a, the fluid 3firsts interacts with the adjustable plasma 4 created between theelectrode 1 and the surface 2 of the liquid 3. Thereafter the plasmainfluenced or conditioned fluid 3, having been changed (e.g.,conditioned, modified, or prepared) by the adjustable plasma 4,thereafter communicates with the electrode 5 thus permitting variouselectrochemical reactions to occur, such reactions being influenced bythe state (e.g., chemical composition, physical or crystal structure,excited state(s), etc., of the fluid 3 (and constituents within thefluid 3)) discussed in greater detail elsewhere herein. An alternativeembodiment is shown in FIG. 8 b. This embodiment essentially correspondsin general arrangement to those embodiments shown in FIGS. 3 b and 4 b.In this embodiment, the fluid 3 first communicates with the electrode 5,and thereafter the fluid 3 communicates with the adjustable plasma 4created between the electrode 1 and the surface 2 of the liquid 3.

FIG. 8 c shows a cross-sectional perspective view of two electrodes 5 aand 5 b (corresponding to the embodiments shown in FIGS. 3 c and 4 c)wherein the longitudinal flow direction “F” of the fluid 3 contacts thefirst electrode 5 a and thereafter contacts the second electrode 5 b inthe direction “F” of fluid flow.

Likewise, FIG. 8 d is a cross-sectional perspective view and correspondsto the embodiments shown in FIGS. 3 d and 4 d. In this embodiment, thefluid 3 communicates with a first adjustable plasma 4 a created by afirst electrode 1 a and thereafter communicates with a second adjustableplasma 4 b created between a second electrode 1 b and the surface 2 ofthe fluid 3.

FIG. 9 a shows a cross-sectional perspective view and corresponds to theelectrode configuration shown in FIG. 7 b (and generally to theelectrode configuration shown in FIGS. 3 a and 4 a but is rotated 90degrees relative thereto). All of the electrode configurations shown inFIGS. 9 a-9 d are situated such that the electrode pairs shown arelocated substantially at the same longitudinal point along the troughmember 30, as in FIG. 7 b.

Likewise, FIG. 9 b corresponds generally to the electrode configurationshown in FIGS. 3 b and 4 b, and is rotated 90 degrees relative to theconfiguration shown in FIG. 8 b.

FIG. 9 c shows an electrode configuration corresponding generally toFIGS. 3 c and 4 c, and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8 c.

FIG. 9 d shows an electrode configuration corresponding generally toFIGS. 3 d and 4 d and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8 d.

The electrode configurations shown generally in FIGS. 7, 8 and 9, allcan create different results (e.g., different conditioning effects forthe fluid 3, different pH's in the fluid 3, different sizes, shapes,and/or amounts of particulate matter found in the fluid 3, differentfunctioning of the fluid/nanoparticle combination, etc.) as a functionof a variety of features including the electrode orientation andposition relative to the fluid flow direction “F”, the number ofelectrode pairs provided and their positioning in the trough member 30relative to each other. Further, the electrode compositions, size,specific shapes, number of different types of electrodes provided,voltage applied, amperage applied, AC source, DC source, RF source,electrode polarity, etc., can all influence the properties of the liquid3 (and/or constituents contained in the liquid 3) as the liquid 3 flowspast these electrodes 1, 5 and hence resultant properties of thematerials (e.g., the nanoparticle solution) produced therefrom.Additionally, the liquid-containing trough member 30, in some preferredembodiments, contains a plurality of the electrode combinations shown inFIGS. 7, 8 and 9. These electrode assemblies may be all the sameconfiguration or may be a combination of various different electrodeconfigurations (discussed in greater detail elsewhere herein). Moreover,the electrode configurations may sequentially communicate with the fluid“F” or may simultaneously, or in parallel communicate with the fluid“F”. Different exemplary and preferred electrode configurations areshown in additional figures later herein and are discussed in greaterdetail later herein in conjunction with different nanoparticles andnanoparticle/solutions produced therefrom.

FIG. 10 a shows a cross-sectional view of the liquid containing troughmember 30 shown in FIGS. 7, 8 and 9. This trough member 30 has across-section corresponding to that of a rectangle or a square and theelectrodes (not shown in FIG. 10 a) can be suitably positioned therein.

Likewise, several additional alternative cross-sectional embodiments forthe liquid-containing trough member 30 are shown in FIGS. 10 b, 10 c, 10d and 10 e. The distance “S” and “S′” for the preferred embodiment shownin each of FIGS. 10 a-10 e measures, for example, between about 1″ andabout 3″ (about 2.5 cm-7.6 cm). The distance “M” ranges from about 2″ toabout 4″ (about 5 cm-10 cm). The distance “R” ranges from about 1/16″-½″to about 3″ (about 1.6 mm-3 mm to about 76 mm). All of these embodiments(as well as additional configurations that represent alternativeembodiments are within the metes and bounds of this inventivedisclosure) can be utilized in combination with the other inventiveaspects of the invention. It should be noted that the amount of liquid 3contained within each of the liquid containing trough members 30 is afunction not only of the depth “d”, but also a function of the actualcross-section. Briefly, the amount of fluid 3 present in and around theelectrode(s) 1 and 5 can influence one or more effects of the adjustableplasma 4 upon the liquid 3 as well as the electrochemical interaction(s)of the electrode 5 with the liquid 3. These effects include not onlyadjustable plasma 4 conditioning effects (e.g., interactions of theplasma electric and magnetic fields, interactions of the electromagneticradiation of the plasma, creation of various chemical species (e.g.,Lewis acids, Bronsted-Lowry acids) within the liquid, pH changes, etc.)upon the liquid 3, but also the concentration or interaction of theadjustable plasma 4 with the liquid 3. Similarly, the influence of manyaspects of the electrode 5 on the liquid 3 (e.g., electrochemicalinteractions) is also, at least partially, a function of the amount ofliquid juxtaposed to the electrode(s) 5. Further, strong electric andmagnetic field concentrations will also effect the interaction of theplasma 4 with the liquid 3 as well as effect the interaction of theelectrode 5 with the liquid 3. Some important aspects of these importantinteractions are discussed in greater detail later herein. Further, atrough member 30 may comprise more than one cross-sectional shape alongits entire longitudinal length. The incorporation of multiplecross-sectional shapes along the longitudinal length of a trough member30 can result in, for example, varying the field or concentration orreaction effects being produced by the inventive embodiments disclosedherein (discussed in greater detail elsewhere herein). Further, a troughmember 30 may not be linear or “I-shaped”, but rather may be “Y-shaped”or “Ψ-shaped”, with each portion of the “Y” (or “Ψ”) having a different(or similar) cross-sectional shape and/or set of dimensions.

FIG. 11 a shows a perspective view of one embodiment of substantiallyall of the trough member 30 shown in FIG. 10 b including an inletportion or inlet end 31 and an outlet portion or outlet end 32. The flowdirection “F” discussed in other figures herein corresponds to a liquidentering at or near the end 31 (e.g., utilizing an appropriate means fordelivering fluid into the trough member 30 at or near the inlet portion31) and exiting the trough member 30 through the end 32. FIG. 11 b showsthe trough member 30 of FIG. 11 a containing three control devices 20 a,20 b and 20 c removably attached to the trough member 30. Theinteraction and operations of the control devices 20 a, 20 b and 20 ccontaining the electrodes 1 and/or 5 are discussed in greater detaillater herein. However, in a preferred embodiment of the invention, thecontrol devices 20, can be removably attached to a top portion of thetrough member 30 so that the control devices 20 are capable of beingpositioned at different positions along the trough member 30, therebyaffecting certain processing parameters, constituents produced,reactivity of constituents produced, as well as nanoparticle(s)/fluid(s)produced therefrom.

FIG. 11 c shows a perspective view of an atmosphere control device cover35′. The atmosphere control device or cover 35′ has attached thereto aplurality of control devices 20 a, 20 b and 20 c controllably attachedto electrode(s) 1 and/or 5. The cover 35′ is intended to provide theability to control the atmosphere within and/or along a substantialportion of (e.g., greater than 50% of) the longitudinal direction of thetrough member 30, such that any adjustable plasma(s) 4 created betweenany electrode(s) 1 and surface 2 of the liquid 3 can be a function ofvoltage, current, current density, polarity, etc. (as discussed in moredetail elsewhere herein) as well as a controlled atmosphere (alsodiscussed in more detail elsewhere herein).

FIG. 11 d shows the apparatus of FIG. 11 c including an additionalsupport means 34 for supporting the trough member 30 (e.g., on anexterior portion thereof), as well as supporting (at least partially)the control devices 20 (not shown in FIG. 11 d). It should be understoodby the reader that various details can be changed regarding, forexample, the cross-sectional shapes shown for the trough member 30,atmosphere control(s) (e.g., the cover 35′) and external support means(e.g., the support means 34) which are within the metes and bounds ofthis disclosure, some of which are discussed in greater detail laterherein.

FIG. 11 e shows an alternative configuration for the trough member 30.Specifically, the trough member 30 is shown in perspective view and is“Y-shaped”. Specifically, the trough member 30 comprises top portions 30a and 30 b and a bottom portion 30 o. Likewise, inlets 31 a and 31 b areprovided along with outlet 32. A portion 30 d corresponds to the pointwhere 30 a and 30 b meet 30 o.

FIG. 11 f shows the same “Y-shaped” trough member shown in FIG. 11 e,except that the portion 30 d of FIG. 11 e is now shown as a mixingsection 30 d′. In this regard, certain constituents manufactured orproduced in the liquid 3 in one or all of, for example, the portions 30a, 30 b and/or 30 c, may be desirable to be mixed together at the point30 d (or 30 d′). Such mixing may occur naturally at the intersection 30d shown in FIG. 11 e (i.e., no specific or special section 30 d′ may beneeded), or may be more specifically controlled at the portion 30 d′. Itshould be understood that the portion 30 d′ could be shaped in anyeffective shape, such as square, circular, rectangular, etc., and be ofthe same or different depth relative to other portions of the troughmember 30. In this regard, the area 30 d could be a mixing zone orsubsequent reaction zone.

FIGS. 11 g and 11 h show a “Ψ-shaped” trough member 30. Specifically, anew portion 30 c has been added. Other features of FIGS. 11 g and 11 hare similar to those features shown in 11 e and 11 f.

It should be understood that a variety of different shapes can exist forthe trough member 30, any one of which can produce desirable results.

FIG. 12 a shows a perspective view of a local atmosphere controlapparatus 35 which functions as a means for controlling a localatmosphere around the electrode sets 1 and/or 5 so that variouslocalized gases can be utilized to, for example, control and/or effectcertain components in the adjustable plasma 4 between electrode 1 andsurface 2 of the liquid 3, as well as influence adjustableelectrochemical reactions at and/or around the electrode(s) 5. Thethrough-holes 36 and 37 shown in the atmosphere control apparatus 35 areprovided to permit external communication in and through a portion ofthe apparatus 35. In particular, the hole or inlet 37 is provided as aninlet connection for any gaseous species to be introduced to the insideof the apparatus 35. The hole 36 is provided as a communication port forthe electrodes 1 and/or 5 extending therethrough which electrodes areconnected to, for example, the control device 20 located above theapparatus 35. Gasses introduced through the inlet 37 can simply beprovided at a positive pressure relative to the local externalatmosphere and may be allowed to escape by any suitable means or pathwayincluding, but not limited to, bubbling out around the portions 39 aand/or 39 b of the apparatus 35, when such portions are caused, forexample, to be at least partially submerged beneath the surface 2 of theliquid 3 (discussed in greater detail later herein). Alternatively, asecond hole or outlet (not shown) can be provided elsewhere in theatmosphere control apparatus 35. Generally, the portions 39 a and 39 bcan break the surface 2 of the liquid 3 effectively causing the surface2 to act as part of the seal to form a localized atmosphere aroundelectrode sets 1 and/or 5. When a positive pressure of a desired gasenters through the inlet port 37, small bubbles can be caused to bubblepast, for example, the portions 39 a and/or 39 b. Alternatively, gas mayexit through an appropriate outlet in the atmosphere control apparatus35.

FIG. 12 b shows a perspective view of first atmosphere control apparatus35 a in the foreground of the trough member 30 contained within thesupport housing 34. A second atmosphere control apparatus 35 b isincluded and shows a control device 20 located thereon. “F” denotes thelongitudinal direction of flow of liquid through the trough member 30.The desirability of locally controlled atmosphere(s) (e.g., ofsubstantially the same chemical constituents, such as air or nitrogen,or substantially different chemical constituents, such as helium andnitrogen) around different electrode sets 1 and/or 5 is discussed ingreater detail later herein.

FIG. 13 shows a perspective view of an alternative atmosphere controlapparatus 38 wherein the entire trough member 30 and support means 34are contained within the atmosphere control apparatus 38. In this case,for example, gas inlet 37 (37′) can be provided along with a gasoutlet(s) 37 a (37 a′). The exact positioning of the gas inlet(s) 37(37′) and gas outlet(s) 37 a (37 a′) on the atmosphere control apparatus38 is a matter of convenience, as well as a matter of the composition ofthe atmosphere contained therein. In this regard, if the gas is heavierthan air or lighter than air, inlet and outlet locations can be adjustedaccordingly. Aspects of these factors are discussed in greater detaillater herein.

FIG. 14 shows a schematic view of the general apparatus utilized inaccordance with the teachings of some of the preferred embodiments ofthe present invention. In particular, this FIG. 14 shows a sideschematic view of the trough member 30 containing a liquid 3 therein. Onthe top of the trough member 30 rests a plurality of control devices 20a-20 d which are, in this embodiment, removably attached thereto. Thecontrol devices 20 a-20 d may of course be permanently fixed in positionwhen practicing various embodiments of the invention. The precise numberof control devices 20 (and corresponding electrode(s) 1 and/or 5 as wellas the configuration(s) of such electrodes) and the positioning orlocation of the control devices 20 (and corresponding electrodes 1and/or 5) are a function of various preferred embodiments of theinvention discussed in greater detail later herein. However, in general,an input liquid 3 (for example water or purified water) is provided to aliquid transport means 40 (e.g., a liquid pump, gravity or liquidpumping means for pumping the liquid 3) such as a peristaltic pump forpumping the liquid water 3 into the trough member 30 at a first-end 31thereof. Exactly how the liquid 3 is introduced is discussed in greaterdetail later herein. The liquid transport means 40 may include any meansfor moving liquids 3 including, but not limited to a gravity-fed orhydrostatic means, a pumping means, a regulating or valve means, etc.However, the liquid transport means 40 should be capable of reliablyand/or controllably introducing known amounts of the liquid 3 into thetrough member 30. Once the liquid 3 is provided into the trough member30, means for continually moving the liquid 3 within the trough member30 may or may not be required. However, a simple means for continuallymoving the liquid 3 includes the trough member 30 being situated on aslight angle θ (e.g., less than a degree to a few degrees for a lowviscosity fluid 3 such as water) relative to the support surface uponwhich the trough member 30 is located. For example, a difference invertical height of less than one inch between an inlet portion 31 and anoutlet portion 32, spaced apart by about 6 feet (about 1.8 meters)relative to the support surface may be all that is required, so long asthe viscosity of the liquid 3 is not too high (e.g., any viscosityaround the viscosity of water can be controlled by gravity flow oncesuch fluids are contained or located within the trough member 30). Inthis regard, FIGS. 15 a and 15 b show two acceptable angles θ₁ and θ₂,respectively, for trough member 30 that can process various viscosities,including low viscosity fluids such as water. The need for a greaterangle θ could be a result of processing a liquid 3 having a viscosityhigher than water; the need for the liquid 3 to transit the trough 30 ata fast rate, etc. Further, when viscosities of the liquid 3 increasesuch that gravity alone is insufficient, other phenomena such asspecific uses of hydrostatic head pressure or hydrostatic pressure canalso be utilized to achieve desirable fluid flow. Further, additionalmeans for moving the liquid 3 along the trough member 30 could also beprovided inside the trough member 30. Such means for moving the fluidinclude mechanical means such as paddles, fans, propellers, augers,etc., acoustic means such as transducers, thermal means such as heaters(which may have additional processing benefits), etc., are alsodesirable for use with the present invention.

FIG. 14 also shows a storage tank or storage vessel 41 at the end 32 ofthe trough member 30. Such storage vessel 41 can be any acceptablevessel and/or pumping means made of one or more materials which, forexample, do not negatively interact with the liquid 3 produced withinthe trough member 30. Acceptable materials include, but are not limitedto plastics such as high density polyethylene (HDPE), glass, metal(s)(such a certain grades of stainless steel), etc. Moreover, while astorage tank 41 is shown in this embodiment, the tank 41 should beunderstood as including a means for distributing or directly bottling orpackaging the fluid 3 processed in the trough member 30.

FIGS. 16 a, 16 b and 16 c show a perspective view of one preferredembodiment of the invention. In these FIGS. 16 a, 16 b and 16 c, eightseparate control devices 20 a-h are shown in more detail. Such controldevices 20 can utilize one or more of the electrode configurations shownin, for example, FIGS. 8 a, 8 b, 8 c and 8 d. The precise positioningand operation of the control devices 20 (and the correspondingelectrodes 1 and/or 5) are discussed in greater detail elsewhere herein.FIG. 16 b includes use of two air distributing or air handling devices(e.g., fans 342 a and 342 b). Similarly, FIG. 16 c includes the use oftwo alternative air distributing or air handling devices 342 c and 342d.

FIG. 17 shows another perspective view of another embodiment of theapparatus according to the present invention wherein six control devices20 a-20 f are rotated approximately 90 degrees relative to the eightcontrol devices 20 a-20 h shown in FIGS. 16 a, 16 b and 16 c. Theprecise location and operation of the control devices 20 and theassociated electrodes 1 and/or 5 are discussed in greater detailelsewhere herein.

FIG. 18 shows a perspective view of the apparatus shown in FIG. 16 a,but such apparatus is now shown as being substantially completelyenclosed by an atmosphere control apparatus 38. Such apparatus 38 is ameans for controlling the atmosphere around the trough member 30, or canbe used to isolate external and undesirable material from entering intothe trough member 30 and negatively interacting therewith. Further, theexit 32 of the trough member 30 is shown as communicating with a storagevessel 41 through an exit pipe 42. Moreover, an exit 43 on the storagetank 41 is also shown. Such exit pipe 43 can be, directed toward anyother suitable means for storage, packing and/or handling the liquid 3(discussed in greater detail herein).

FIGS. 19 a, 19 b, 19 c and 19 d show additional cross-sectionalperspective views of additional electrode configuration embodimentswhich can be used according to the present invention.

In particular, FIG. 19 a shows two sets of electrodes 5 (i.e., 4 totalelectrodes 5 a, 5 b, 5 c and 5 d) located approximately parallel to eachother along a longitudinal direction of the trough member 30 andsubstantially perpendicular (i.e., 60°-90°) to the flow direction “F” ofthe liquid 3 through the trough member 30. In contrast, FIG. 19 b showstwo sets of electrodes 5 (i.e, 5 a, 5 b, 5 c and 5 d) located adjacentto each other along the longitudinal direction of the trough member 30.

In contrast, FIG. 19 c shows one set of electrodes 5 (5 a, 5 b) locatedsubstantially perpendicular to the direction of fluid flow “F” andanother set of electrodes 5 (5 c, 5 d) located substantially parallel tothe direction of the fluid flow “F”. FIG. 19 d shows a mirror image ofthe electrode configuration shown in FIG. 19 c. While each of FIGS. 19a, 19 b, 19 c and 19 d show only electrode(s) 5 it is clear thatelectrode(s) 1 could be substituted for some or all of thoseelectrode(s) 5 shown in each of FIGS. 19 a-19 d, and/or intermixedtherein (e.g., similar to the electrode configurations disclosed inFIGS. 8 a-8 d and 9 a-9 d). These alternative electrode configurations,and some of their associated advantages, are discussed in greater detailherein.

FIGS. 20 a-20 p show a variety of cross-sectional perspective views ofthe various electrode configuration embodiments possible and usable forall those configurations of electrodes 1 and 5 corresponding only to theembodiment shown in FIG. 19 a. In particular, for example, the number ofelectrodes 1 or 5 varies in these FIGS. 20 a-20 p, as well as thespecific locations of such electrode(s) 1 and 5 relative to each other.Of course, these electrode combinations 1 and 5 shown in FIGS. 20 a-20 pcould also be configured according to each of the alternative electrodeconfigurations shown in FIGS. 19 b, 19 c and 19 d (i.e., sixteenadditional figures corresponding to each of FIGS. 19 b, 19 c and 19 d)but additional figures have not been included herein for the sake ofbrevity. Specific advantages of these electrode assemblies, and others,are disclosed in greater detail elsewhere herein.

Each of the electrode configurations shown in FIGS. 20 a-20 p, dependingon the particular run conditions, can result in different productscoming from the mechanisms, apparatuses and processes of the presentinvention. A more detailed discussion of these various configurationsand advantages thereof are discussed in greater detail elsewhere herein.

FIGS. 21 a, 21 b, 21 c and 21 d show cross sectional perspective viewsof additional embodiments of the present invention. The electrodearrangements shown in these FIGS. 21 a-21 d are similar in arrangementto those electrode arrangements shown in FIGS. 19 a, 19 b, 19 c and 19d, respectively. However, in these FIGS. 21 a-21 d a membrane or barrierassembly 50 is also included. In these embodiments of the invention, amembrane 50 is provided as a means for separating different productsmade at or near different electrode sets so that some or all of theproducts made by the set of electrodes 1 and/or 5 on one side of themembrane 50 can be at least partially isolated, or segregated, orsubstantially completely isolated from certain products made at or nearelectrodes 1 and/or 5 on the other side of the membrane 50. Thismembrane means 50 may act as a mechanical barrier, physical barrier,mechano-physical barrier, chemical barrier, electrical barrier, etc.Accordingly, certain products made from a first set of electrodes 1and/or 5 can be at least partially, or substantially completely,isolated from certain products made from a second set of electrodes 1and/or 5. Likewise, additional serially located electrode sets can alsobe similarly situated. In other words, different membrane(s) 50 can beutilized at or near each set of electrodes 1 and/or 5 and certainproducts produced therefrom can be controlled and selectively deliveredto additional electrode sets 1 and/or 5 longitudinally downstreamtherefrom. Such membranes 50 can result in a variety of differentcompositions of the liquid 3 and/or nanoparticles or ions orconstituents present in the liquid 3 produced in the trough member 30(discussed in greater detail herein). For example, different formedcompositions in the liquid 3 can be isolated from each other.

FIG. 22 a shows a perspective cross-sectional view of an electrodeassembly which corresponds to the electrode assembly 5 a, 5 b shown inFIG. 9 c. This electrode assembly can also utilize a membrane 50 forchemical, physical, chemo-physical and/or mechanical separation. In thisregard, FIG. 22 b shows a membrane 50 located between the electrodes 5a, 5 b. It should be understood that the electrodes 5 a, 5 b could beinterchanged with the electrodes 1 in any of the multiple configurationsshown, for example, in FIGS. 9 a-9 c. In the case of FIG. 22 b, themembrane assembly 50 has the capability of isolating partially orsubstantially completely, some or all of the products formed atelectrode 5 a, from some or all of those products formed at electrode 5b. Accordingly, various species formed at either of the electrodes 5 aand 5 b can be controlled so that they can sequentially react withadditional electrode assembly sets 5 a, 5 b and/or combinations ofelectrode sets 5 and electrode sets 1 in the longitudinal flow direction“F” that the liquid 3 undertakes along the longitudinal length of thetrough member 30. Accordingly, by appropriate selection of membrane 50,which products located at which electrode (or subsequent or downstreamelectrode set) can be controlled, manipulated and/or adjusted. In apreferred embodiment where the polarity of the electrodes 5 a and 5 bare opposite, a variety of different products may be formed at theelectrode 5 a relative to the electrode 5 b.

FIG. 22 c shows another different embodiment of the invention in across-sectional schematic view of a completely different alternativeelectrode configuration for electrodes 5 a and 5 b. In this case,electrode(s) 5 a (or of course electrode(s) 1 a) are located above amembrane 50 and electrode(s) 5 b are located below a membrane 50 (e.g.,are substantially completely submerged in the liquid 3). In this regard,the electrode(s), 5 b can comprise a plurality of electrodes or may be asingle electrode running along at least some or the entire longitudinallength of the trough member 30. In this embodiment, certain speciescreated at electrode(s) 5 above the membrane 50 can be different fromcertain species created below the membrane 50 and such species can reactdifferently along the longitudinal length of the trough member 30. Inthis regard, the membrane 50 need not run the entire length of thetrough member 30, but may be present for only a portion of such lengthand thereafter sequential assemblies of electrodes 1 and/or 5 can reactwith the products produced therefrom. It should be clear to the readerthat a variety of additional embodiments beyond those expresslymentioned here would fall within the spirit of the embodiments expresslydisclosed.

FIG. 22 d shows another alternative embodiment of the invention wherebya configuration of electrodes 5 a (and of course electrodes 1) shown inFIG. 22 c are located above a portion of a membrane 50 which extends atleast a portion along the length of a trough member 30 and a secondelectrode (or plurality of electrodes) 5 b (similar to electrode(s) 5 bin FIG. 22 c) run for at least a portion of the longitudinal lengthalong the bottom of the trough member 30. In this embodiment ofutilizing multiple electrodes 5 a, additional operational flexibilitycan be achieved. For example, by splitting the voltage and current intoat least two electrodes 5 a, the reactions at the multiple electrodes 5a can be different from those reactions which occur at a singleelectrode 5 a of similar size, shape and/or composition. Of course thismultiple electrode configuration can be utilized in many of theembodiments disclosed herein, but have not been expressly discussed forthe sake of brevity. However, in general, multiple electrodes 1 and/or 5(i.e., instead of a single electrode 1 and/or 5) can add greatflexibility in products produced according to the present invention.Details of certain of these advantages are discussed elsewhere herein.

FIG. 23 a is a cross-sectional perspective view of another embodiment ofthe invention which shows a set of electrodes 5 corresponding generallyto that set of electrodes 5 shown in FIG. 19 a however, the differencebetween the embodiment of FIG. 23 a is a third set of electrode(s) 5 e,5 f have been provided in addition to those two sets of electrodes 5 a,5 b, 5 c and 5 d shown in FIG. 19 a. Of course, the sets of electrodes 5a, 5 b, 5 c, 5 d, 5 e and 5 f can also be rotated 90 degrees so theywould correspond roughly to those two sets of electrodes shown in FIG.19 b. Additional figures showing additional embodiments of those sets ofelectrode configurations have not been included here for the sake ofbrevity.

FIG. 23 b shows another embodiment of the invention which alsopermutates into many additional embodiments, wherein membrane assemblies50 a and 50 b have been inserted between the three sets of electrodes 5a,5 b-5 c,5 d and 5 e,5 f. It is of course apparent that the combinationof electrode configuration(s), number of electrode(s) and precisemembrane(s) means 50 used to achieve separation includes manyembodiments, each of which can produce different products when subjectedto the teachings of the present invention. More detailed discussion ofsuch products and operations of these embodiments are discussedelsewhere herein.

FIGS. 24 a-24 e; 25 a-25 e; and 26 a-26 e show cross-sectional views ofa variety of membrane means 50 designs and/or locations that can beutilized according to various embodiments disclosed herein. In each ofthese embodiments, the membrane means 50 provide a means for separatingone or more products made at one or more electrode assemblies 1/5.

DETAILED DESCRIPTION OF THE DRAWINGS

FIGS. 1 a, 1 b and 1 c show schematic cross-sectional views of a manualelectrode assembly according to the present invention.

FIGS. 2 a and 2 b show schematic cross-sectional views of an automaticelectrode assembly according to the present invention.

FIGS. 3 a-3 d show four alternative electrode configurations for theelectrodes 1 and 5 controlled by an automatic device.

FIGS. 4 a-4 d show four alternative electrode configurations for theelectrodes 1 and 5 which are manually controlled.

FIGS. 5 a-5 e show five different representative embodiments ofconfigurations for the electrode 1.

FIG. 6 shows a cross-sectional schematic view of plasmas producedutilizing one specific configuration of electrode 1.

FIGS. 7 a and 7 b show a cross-sectional perspective view of twoelectrode assemblies utilized.

FIGS. 8 a-8 d show schematic perspective views of four differentelectrode assemblies corresponding to those electrode assemblies shownin FIGS. 3 a-3 d, respectively.

FIGS. 9 a-9 d show schematic perspective views of four differentelectrode assemblies corresponding to those electrode assemblies shownin FIGS. 4 a-4 d, respectively.

FIGS. 10 a-10 e show cross-sectional views of various trough members 30.

FIGS. 11 a-11 h show perspective views of various trough members andatmosphere control and support devices.

FIGS. 12 a and 12 b show various atmosphere control devices for locallycontrolling atmosphere around electrode sets 1 and/or 5.

FIG. 13 shows an atmosphere control device for controlling atmospherearound the entire trough member 30.

FIG. 14 shows a schematic cross-sectional view of a set of controldevices 20 located on a trough member 30 with a liquid 3 flowingtherethrough.

FIGS. 15 a and 15 b show schematic cross-sectional views of variousangles θ_(i) and θ₂ for the trough member 30.

FIGS. 16 a, 16 b and 16 c show perspective views of various controldevices 20 containing electrode assemblies 1 and/or 5 thereon located ontop of a trough member 30.

FIG. 17 shows a perspective view of various control devices 20containing electrode assemblies 1 and/or 5 thereon located on top of atrough member 30.

FIG. 18 shows a perspective view of various control devices 20containing electrode assemblies 1 and/or 5 thereon located on top of atrough member 30 and including an enclosure 38 which controls theenvironment around the entire device and further including a holdingtank 41.

FIGS. 19 a-19 d are perspective schematic views of multiple electrodesets contained within a trough member 30.

FIGS. 20 a-20 p show perspective views of multiple electrode sets 1/5 in16 different possible combinations.

FIGS. 21 a-21 d show four perspective schematic views of possibleelectrode configurations separated by a membrane 50.

FIGS. 22 a-22 d show a perspective schematic views of four differentelectrode combinations separated by a membrane 50.

FIGS. 23 a and 23 b show a perspective schematic view of three sets ofelectrodes and three sets of electrodes separated by two membranes 50 aand 50 b, respectively.

FIGS. 24 a-24 e show various membranes 50 located in variouscross-sections of a trough member 30.

FIGS. 25 a-25 e show various membranes 50 located in variouscross-sections of a trough member 30.

FIGS. 26 a-26 e show various membranes 50 located in variouscross-sections of a trough member 30.

FIG. 27 shows a perspective view of a control device 20.

FIGS. 28 a and 28 b show a perspective view of a control device 20.

FIG. 28 c shows a perspective view of an electrode holder.

FIGS. 28 d-28 l show a variety of perspective views of different controldevices 20, with and without localized atmospheric control devices.

FIG. 29 shows a perspective view of a thermal management deviceincluding a refractory member 29 and a heat sink 28.

FIG. 30 shows a perspective view of a control device 20.

FIG. 31 shows a perspective view of a control device 20.

FIGS. 32 a, 32 b and 32 c show AC transformer electrical wiring diagramsfor use with different embodiments of the invention.

FIG. 33 a shows a schematic view of a transformer and FIGS. 33 b and 33c show schematic representations of two sine waves in phase and out ofphase, respectively.

FIGS. 34 a, 34 b and 34 c each show schematic views of eight electricalwiring diagrams for use with 8 sets of electrodes.

FIG. 35 shows a schematic view of an electrical wiring diagram utilizedto monitor voltages from the outputs of a secondary coil of atransformer.

FIGS. 36 a, 36 b and 36 c show schematic views of wiring diagramsassociated with a Velleman K8056 circuit relay board.

FIG. 37 a shows a bar chart of various target and actual averagevoltages applied to 16 different electrodes in an 8 electrode set usedin Example 1 to manufacture silver-based nanoparticles and nanoparticlesolutions.

FIGS. 37 b-37 i show actual voltages applied as a function of time forthe 16 different electrodes used in Example 1.

FIG. 38 a shows a bar chart of various target and actual averagevoltages applied to 16 different electrodes in an 8 electrode set usedin Example 2 to manufacture silver-based nanoparticles and nanoparticlesolutions.

FIGS. 38 b-38 i show actual voltages applied as a function of time forthe 16 different electrodes used in Example 2

FIG. 39 a shows a bar chart of various target and actual averagevoltages applied to 16 different electrodes in an 8 electrode set usedin Example 3 to manufacture silver-based nanoparticles and nanoparticlesolutions.

FIGS. 39 b-39 i show actual voltages applied as a function of time for16 different electrodes used in Example 3.

FIG. 40 a shows a bar chart of various target and actual averagevoltages applied to 16 different electrodes in an 8 electrode set usedin Example 4 to manufacture zinc-based nanoparticles and nanoparticlesolutions.

FIGS. 40 b-40 i show actual voltages applied as a function of time forthe 16 different electrodes used in Example 4.

FIG. 41 a shows a bar chart of various target and actual averagevoltages applied to 16 different electrodes in an 8 electrode set usedin Example 5 to manufacture copper-based nanoparticles and nanoparticlesolutions.

FIGS. 41 b-41 i show actual voltages applied as a function of time forthe 16 different electrodes used in Example 5.

FIGS. 42 a-e are SEM-EDS plots of the materials made in each of Examples1-5, respectively.

FIGS. 42 f-o correspond to 10 different solutions GR1-GR10 madeutilizing the raw materials of Examples 1-5 (i.e., made according toTable 8 and Table 9).

FIGS. 43 a(i-iv)-43 e(i-iv) are SEM photomicrographs at 4 differentmagnifications in each Figure corresponding to the raw materials ofExamples 1-5, respectively.

FIGS. 43 f(i-iv)-43 o(i-iv) are SEM photomicrographs at 4 differentmagnifications in each Figure corresponding to the solutions GR1-GR10disclosed in Table 8 and Table 9. FIGS. 43 p(i) 43 p(iii) disclose threedifferent magnification TEM photomicrographs of a silver constituentmade corresponding to the production parameters used to manufactureAT031.

FIGS. 43 q(i) 43 q(vi) disclose six different TEM photomicrographs takenat three different magnifications of a silver constituent madecorresponding to the production parameters used to manufacture AT060.

FIGS. 43 r(i) 43 r(ii) disclose two different TEM photomicrographs takenat two different magnifications of a zinc constituent made according tothe production parameters used to manufacture BT006.

FIGS. 43 s(i) 43 s(v) disclose five different TEM photomicrographs takenat three different magnifications of a solution GR5.

FIGS. 43 t(i) 43 t(x) disclose ten different TEM photomicrographs takenat three different magnifications of a solution GR8.

FIG. 44 a shows 5 UV-Vis spectra of the raw materials made according toExamples 1-5.

FIGS. 44 b-44 e show UV-Vis spectra of the 10 different solutionsGR1-GR10 shown in Table 8 and Table 9 made with the raw materialsaccording to Examples 1-5.

FIG. 45 shows a raman spectra of each of the 10 solutions GR1-GR10 shownin Table 8 and Table 9.

FIG. 46 shows biological Bioscreen results for E. coli against the rawmaterials of Examples 1-5 and the solutions GR1-GR10 shown in Table 8and Table 9.

FIG. 47 shows biological minimum inhibitory concentration (“MIC”)results obtained with a Bioscreen device utilizing GR3 against e. coli;optimal density is plotted as a function of time.

FIG. 48 shows biological minimum inhibitory concentration (“MIC”)results obtained with a Bioscreen device utilizing GR8 against e. coli;optimal density is plotted as a function of time.

FIG. 49 shows biological results from a Bioscreen device utilizing theraw material made from Example 2 combined with various varying amountsof the raw materials made in Example 4; optimal density is plotted as afunction of time.

FIGS. 50 a-50 d show biological results of the raw material made inExample 2 obtained with a Bioscreen device with various amounts oftreated water added thereto; optimal density is plotted as a function oftime.

FIGS. 51 a-51 h show various cellular growth and cytotoxicity curves forsolutions GR3, GR5, GR8 and GR9 against both mini-pig kidney fibroblastcells and murine liver epithelial cells; the amount of fluorescencerelative to control (100%) cells is plotted against increasing amountsof nanoparticles.

FIGS. 52 a-52 f show cytotoxicity (LD₅₀) results (curves) for GR3, GR5and GR8 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIGS. 53 a-53 h show LD₅₀ results (curves) for GR3, GR5, GR8 and GR9against mini-pig kidney fibroblast cells; the amount of fluorescencerelative to control (100%) cells is plotted against increasing amountsof nanoparticles.

FIG. 54 shows biological results from a Bioscreen device for theperformance of solution GR5, as formed in Table 8 and, compared to afreeze-dried and rehydrated GR5; optimal density is plotted as afunction of time.

FIGS. 55 a-55 c show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 6 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 56 a-56 h show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 7 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 57 a-57 b show Dynamic Light Scattering measurements for Example7.

FIGS. 58 a-58 g are SEM photomicrographs of dried samples made accordingto Example 7.

FIGS. 59 a-59 c are UV-Vis Spectra taken of the liquid samples madeaccording to Example 7.

FIG. 60 shows biological Bioscreen results for the samples madeaccording to Example 7.

FIGS. 61 a-61 c show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 8 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 62 a-62 c show Dynamic Light Scattering measurements for Example8.

FIG. 63 shows biological Bioscreen results for the Example 8.

FIGS. 64 a-64 e show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 9 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 65 a-65 b show a perspective view of a spectra collectionapparatus used in Example 9.

FIGS. 66 a-66 e show spectra collected from Example 9.

FIGS. 67 a-67 f show representative spectra known in the art.

FIG. 68 shows biological Bioscreen results for the Example 9.

FIG. 69 show bar charts of various target and actual average voltagesapplied to different electrodes used in Example 10 to manufacturesilver-based nanoparticles and nanoparticle solutions.

FIGS. 70 a-70 c show spectra collected from Example 10.

FIGS. 71 a-71 c show spectra collected from Example 10.

FIGS. 72 a-72 c show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIGS. 73 a-73 b show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIG. 74 a-74 b show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIG. 75 shows a bar chart of various target and actual average voltagesapplied to different electrodes used in Example 11 to manufacturesilver-based nanoparticles and nanoparticle solutions.

FIGS. 76 a-76 b show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIGS. 77 a-77 b show biological Bioscreen results for the Example 11.

FIGS. 78 a-78 b show biological Bioscreen results for the Example 12.

FIGS. 79 a-79 c show biological Bioscreen results for the Example 12.

FIGS. 80 a-80 f show Dynamic Light Scattering measurements for Example12.

FIGS. 81 a-81 e show Dynamic Light Scattering measurements for Example12.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The embodiments disclosed herein relate generally to novel methods andnovel devices for the continuous manufacture of a variety ofconstituents in a liquid including nanoparticles, andnanoparticle/liquid(s) solution(s). The nanoparticles produced in thevarious liquids can comprise a variety of possible compositions, sizesand shapes, conglomerates, composites and/or surface morphologies whichexhibit a variety of novel and interesting physical, catalytic,biocatalytic and/or biophysical properties. The liquid(s) used and/orcreated/modified during the process play an important role in themanufacturing of and/or the functioning of the nanoparticles and/ornanoparticle/liquid(s) solutions(s). The atmosphere(s) used play animportant role in the manufacturing and/or functioning of thenanoparticle and/or nanoparticle/liquid(s) solution(s). Thenanoparticles are caused to be present (e.g., created) in at least oneliquid (e.g., water) by, for example, preferably utilizing at least oneadjustable plasma (e.g., formed in one or more atmosphere(s)), whichadjustable plasma communicates with at least a portion of a surface ofthe liquid. The power source(s) used to create the plasma(s) play(s) animportant role in the manufacturing of and/or functioning of thenanoparticles and/or nanoparticle/liquid(s) solution(s). For example,the voltage, amperage, polarity, etc., all can influence processingand/or final properties of produced products. Metal-based electrodes ofvarious composition(s) and/or unique configurations are preferred foruse in the formation of the adjustable plasma(s), but non-metallic-basedelectrodes can also be utilized. Utilization of at least one subsequentand/or substantially simultaneous adjustable electrochemical processingtechnique is also preferred. Metal-based electrodes of variouscomposition(s) and/or unique configurations are preferred for use in theadjustable electrochemical processing technique(s).

Adjustable Plasma Electrodes and Adjustable Electrochemical Electrodes

An important aspect of one embodiment of the invention involves thecreation of an adjustable plasma, which adjustable plasma is locatedbetween at least one electrode (or plurality of electrodes) positionedabove at least a portion of the surface of a liquid and at least aportion of the surface of the liquid itself. The surface of the liquidis in electrical communication with at least one second electrode (or aplurality of second electrodes). This configuration has certaincharacteristics similar to a dielectric barrier discharge configuration,except that the surface of the liquid is an active participant in thisconfiguration.

FIG. 1 a shows a partial cross-sectional view of one embodiment of aelectrode 1 having a triangular shape located a distance “x” above thesurface 2 of a liquid 3 flowing, for example, in the direction “F”. Theelectrode 1 shown is an isosceles triangle, but may be shaped as a rightangle or equilateral triangle as well. An adjustable plasma 4 isgenerated between the tip or point 9 of the electrode 1 and the surface2 of the liquid 3 when an appropriate power source 10 is connectedbetween the point source electrode 1 and the electrode 5, whichelectrode 5 communicates with the liquid 3 (e.g., is at least partiallybelow the surface 2 (e.g., bulk surface or effective surface) of theliquid 3). It should be noted that under certain conditions the tip 9′of the electrode 5 may actually be located physically slightly above thebulk surface 2 of the liquid 3, but the liquid still communicates withthe electrode through a phenomena known as “Taylor cones” therebycreating an effective surface 2′. Taylor cones are discussed in U.S.Pat. No. 5,478,533, issued on Dec. 26, 1995 to Inculet, entitled Methodand Apparatus for Ozone Generation and Treatment of Water; the subjectmatter of which is herein expressly incorporated by reference. In thisregard, FIG. 1 b shows an electrode configuration similar to that shownin FIG. 1 a, except that a Taylor cone “T” is utilized to create aneffective surface 2′ to achieve electrical connection between theelectrode 5 and the surface 2 (2′) of the liquid 3. Taylor cones arereferenced in the Inculet patent as being created by an “impressedfield”. In particular, Taylor cones were first analyzed by Sir GeoffreyTaylor in the early 1960's wherein Taylor reported that the applicationof an electrical field of sufficient intensity will cause a waterdroplet to assume a conical formation. It should be noted that Taylorcones, while a function of the electric field, are also a function ofthe conductivity of the fluid. Accordingly, as conductivity changes, theshape and or intensity of a Taylor cone can also change. Accordingly,Taylor cones of various intensity can be observed near tips 9′ atelectrode(s) 5 of the present invention as a function of not only theelectric field which is generated around the electrode(s) 5, but also isa function of constituents in the liquid 3 (e.g., conductiveconstituents provided by, for example, the adjustable plasma 4) andothers. Further, electric field changes are also proportional to theamount of current applied.

The adjustable plasma region 4, created in the embodiment shown in FIG.1 a, can typically have a shape corresponding to a cone-like structurefor at least a portion of the process, and in some embodiments of theinvention, can maintain such cone-like shape for substantially all ofthe process. In other embodiments, the shape of the adjustable plasmaregion 4 may be shaped more like lightning bolts. The volume, intensity,constituents (e.g., composition), activity, precise locations, etc., ofthe adjustable plasma(s) 4 will vary depending on a number of factorsincluding, but not limited to, the distance “x”, the physical and/orchemical composition of the electrode 1, the shape of the electrode 1,the location of the electrode 1 relative to other electrode(s) 1 locatedupstream from the electrode 1, the power source 10 (e.g., DC, AC,rectified AC, polarity of DC and/or rectified AC, RF, etc.), the powerapplied by the power source (e.g., the volts applied, the amps applied,etc.) the electric and/or magnetic fields created at or near the plasma4, the composition of the naturally occurring or supplied gas oratmosphere between and/or around the electrode 1 and the surface 2 ofthe liquid 3, temperature, pressure, flow rate of the liquid 3 in thedirection “F”, composition of the liquid 3, conductivity of the liquid3, cross-sectional area (e.g., volume) of the liquid near and around theelectrodes 1 and 5 (e.g., the amount of time the liquid 3 is permittedto interact with the adjustable plasma 4 and the intensity of suchinteractions), the presence of atmosphere flow (e.g., air flow) at ornear the surface 2 of the liquid 3 (e.g., cooling fan(s) or atmospheremovement means provided), etc. Specifically, for example, the maximumdistance “x” that can be utilized for the adjustable plasma 4 is wheresuch distance “x” corresponds to, for example, the breakdown electricfield “E_(c)” shown in Equation 1. In other words, achieving breakdownof the gas or atmosphere provided between the tip 9 of the electrode 1and the surface 2 of the liquid 3. If the distance “x” exceeds themaximum distance required to achieve electric breakdown (“E_(c)”), thenno plasma 4 will be observed absent the use of additional techniques orinteractions. However, whenever the distance “x” is equal to or lessthan the maximum distance required to achieve the formation of theadjustable plasma 4, then various physical and/or chemical adjustmentsof the plasma 4 can be made. Such changes will include diameter of theplasma 4 at the surface 2 of the liquid 3, intensity (e.g., brightnessand/or strength and/or reactivity) of the plasma 4, the strength of theelectric wind created by the plasma 4 and blowing toward the surface 2of the liquid 3, etc.

The composition of the electrode 1 can also play an important role inthe formation of the adjustable plasma 4. For example, a variety ofknown materials are suitable for use as the electrode(s) 1 of theembodiments disclosed herein. These materials include metals such asplatinum, gold, silver, zinc, copper, titanium, and/or alloys ormixtures thereof, etc. However, the electrode(s) 1 (and 5) can be madeof any suitable material which may comprise metal(s) (e.g., includingappropriate oxides, carbides, nitrides, carbon, silicon and mixtures orcomposites thereof, etc.). Still further, alloys of various metals arealso desirable for use with the present invention. Specifically, alloyscan provide chemical constituents of different amounts, intensitiesand/or reactivities in the adjustable plasma 4 resulting in, forexample, different properties in and/or around the plasma 4 and/ordifferent constituents within the liquid 3. For example, differentspectra can be emitted from the plasma 4, different fields can beemitted from the plasma 4, etc. Thus, the plasma 4 can be involved inthe formation of a variety of different nanoparticles and/ornanoparticle/solutions and/or desirable constituents, or intermediate(s)present in the liquid 3 required to achieve desirable end products.Still further, it is not only the chemical composition and shapefactor(s) of the electrode(s) 1, 5 that play a role in the formation ofthe adjustable plasma 4, but also the manor in which any electrode(s) 1,5 have been manufactured can also influence the performance of theelectrode(s) 1, 5. In this regard, the precise shaping technique(s)including forging, drawing and/or casting technique(s) utilized to fromthe electrode(s) 1, 5 can have an influence on the chemical and/orphysical activity of the electrode(s) 1, 5, including thermodynamicand/or kinetic issues.

The creation of an adjustable plasma 4 in, for example, air above thesurface 2 of a liquid 3 (e.g., water) will, typically, produce at leastsome ozone, as well as certain amounts of a variety of nitrogen-basedcompounds and other components. Various exemplary materials can beproduced in the adjustable plasma 4 and include a variety of materialsthat are dependent on a number of factors including the atmospherebetween the electrode 1 and the surface 2 of the liquid 3. To assist inunderstanding the variety of species that are possibly present in theplasma 4 and/or in the liquid 3 (when the liquid comprises water),reference is made to a 15 Jun. 2000 thesis by Wilhelmus Frederik LaurensMaria Hoeben, entitled “Pulsed corona-induced degradation of organicmaterials in water”, the subject matter of which is expressly hereinincorporated by reference. The work in the aforementioned thesis isdirected primarily to the creation of corona-induced degradation ofundesirable materials present in water, wherein such corona is referredto as a pulsed DC corona. However, many of the chemical speciesreferenced therein, can also be present in the adjustable plasma 4 ofthe embodiments disclosed herein, especially when the atmosphereassisting in the creation of the adjustable plasma 4 comprises humid airand the liquid 3 comprises water. In this regard, many radicals, ionsand meta-stable elements can be present in the adjustable plasma 4 dueto the dissociation and/or ionization of any gas phase molecules oratoms present between the electrode 1 and the surface 2. When humidityin air is present and such humid air is at least a major component ofthe atmosphere “feeding” the adjustable plasma 4, then oxidizing speciessuch as hydroxyl radicals, ozone, atomic oxygen, singlet oxygen andhydropereoxyl radicals can be formed. Still further, amounts of nitrogenoxides like NO_(x) and N₂O can also be formed. Accordingly, Table 1lists some of the reactants that could be expected to be present in theadjustable plasma 4 when the liquid 3 comprises water and the atmospherefeeding or assisting in providing raw materials to the adjustable plasma4 comprises humid air.

TABLE 1 Reaction/Species Equation H₂O + e⁻ → OH + H + e⁻ dissociation 2H₂O + e⁻ → H₂O₊ + 2e⁻ ionization 3 H₂O₊ + H₂O → H₃O₊ + OH dissociation 4N₂ + e⁻ → N_(2*) + e⁻ excitation 5 O₂ + e⁻ → O_(2*) + e⁻ excitation 6N₂ + e⁻ → 2N + e⁻ dissociation 7 O₂ + e⁻ → 2O + e⁻ dissociation 8 N₂ +e⁻ → N₂₊ + 2e⁻ ionization 9 O₂ + e⁻ → O₂₊ + 2e⁻ ionization 10 O₂ + e⁻ →O²⁻ attachment 11 O₂ + e⁻ → O⁻ + O dissociative attachment 12 O₂ + O →O₃ association 13 H + O₂ → HO₂ association 14 H + O₃ → HO₃ association15 N + O → NO association 16 NO + O → NO₂ association 17 N₂ + O²⁻ → 2NOrecombination 18 N₂ + O → N₂O association 19

An April, 1995 article, entitled “Electrolysis Processes in D.C. CoronaDischarges in Humid Air”, written by J. Lelievre, N. Dubreuil and J.-L.Brisset, and published in the J. Phys. III France 5 on pages 447-457therein (the subject matter of which is herein expressly incorporated byreference) was primarily focused on DC corona discharges and noted thataccording to the polarity of the active electrode, anions such asnitrites and nitrates, carbonates and oxygen anions were the prominentions at a negative discharge; while protons, oxygen and NO_(x) cationswere the major cationic species created in a positive discharge.Concentrations of nitrites and/or nitrates could vary with currentintensity. The article also disclosed in Table I therein (i.e., Table 2reproduced herein) a variety of species and standard electrodepotentials which are capable of being present in the DC plasmas createdtherein. Accordingly, one would expect such species as being capable ofbeing present in the adjustable plasma(s) 4 of the present inventiondepending on the specific operating conditions utilized to create theadjustable plasma(s) 4.

TABLE 2 O₃/O₂ [2.07] NO₃ ⁻/N₂ [1.24] HO₂ ⁻/OH⁻ [0.88] N₂/NH₄ ⁺ [0.27]HN₃/NH₄ ⁺ [1.96] O₂/H₂O [1.23] NO₃ ⁻/N₂O₄ [0.81] O₂/HO₂ ⁻ [−0.08]H₂O₂/H₂O [1.77] NO₃ ⁻/N₂O [1.11] NO₃ ⁻/NO₂ [0.81] CO₂/CO [−0.12] N₂O/N₂[1.77] N₂O₄/HNO₂ [1.07] NO/H₂N₂O₂ [0.71] CO₂/HCO₂H [−0.2] NO/N₂O [1.59]HNO₂/NO [0.98] O₂/H₂O₂ [0.69] N₂/N₂H₅ ⁺ [−0.23] NO⁺/NO [1.46] NO₃ ⁻/NO[0.96] NO₃ ⁻/NO₂ ⁻ [0.49] CO₂/H₂C₂O₄ [−0.49] H₃NOH⁺/ [1.42] NO₃ ⁻/HNO₂[0.94] O₂/OH⁻ [0.41] N₂H₅ ⁺ H₂O/e_(aq.) [−2.07] N₂H₅/NH₄ ⁺ [1.27]

An article published 15 Oct. 2003, entitled, “Optical and electricaldiagnostics of a non-equilibrium air plasma”, authored by XinPei Lu,Frank Leipold and Mounir Laroussi, and published in the Journal ofPhysics D: Applied Physics, on pages 2662-2666 therein (the subjectmatter of which is herein expressly incorporated by reference) focusedon the application of AC (60 Hz) high voltage (<20 kV) to a pair ofparallel electrodes separated by an air gap. One of the electrodes was ametal disc, while the other electrode was a surface of water.Spectroscopic measurements performed showed that light emission from theplasma was dominated by OH (A-X, N₂ (C-B) and N₂ ⁺ (B-X) transitions.The spectra from FIG. 4 a therefrom have been reproduced herein as FIG.67 a.

An article by Z. Machala, et al., entitled, “Emission spectroscopy ofatmospheric pressure plasmas for bio-medical and environmentalapplications”, published in 2007 in the Journal of MolecularSpectroscopy, discloses additional emission spectra of atmosphericpressure plasmas. The spectra from FIGS. 3 and 4 therefrom have beenreproduced as FIGS. 67 b and 67 c.

An article by M. Laroussi and X. Lu, entitled, “Room-temperatureatmospheric pressure plasma plume for biomedical applications”,published in 2005 in Applied Physics Letters, discloses emission spectrafro OH, N₂, N₂ ⁺, He and O. The spectra from FIG. 4 therein has beenreproduced as FIGS. 67 d, 67 e and 67 f.

Also known in the art is the generation of ozone by pulsed-coronadischarge over a water surface as disclosed by Petr Lukes, et al, in thearticle, “Generation of ozone by pulsed corona discharge over watersurface in hybrid gas-liquid electrical discharge reactor”, published inJ. Phys. D: Appl. Phys. 38 (2005) 409-416 (the subject matter of whichis herein expressly incorporated by reference). Lukes, et al, disclosethe formation of ozone by pulse-positive corona discharge generated in agas phase between a planar high voltage electrode (made from reticulatedvitreous carbon) and a water surface, said water having an immersedground stainless steel “point” mechanically-shaped electrode locatedwithin the water and being powered by a separate electrical source.Various desirable species are disclosed as being formed in the liquid,some of which species, depending on the specific operating conditions ofthe embodiments disclosed herein, could also be expected to be present.

Further, U.S. Pat. No. 6,749,759 issued on Jun. 15, 2004 to Denes, etal, and entitled Method for Disinfecting a Dense Fluid Medium in a DenseMedium Plasma Reactor (the subject matter of which is herein expresslyincorporated by reference), discloses a method for disinfecting a densefluid medium in a dense medium plasma reactor. Denes, et al, disclosedecontamination and disinfection of potable water for a variety ofpurposes. Denes, et al, disclose various atmospheric pressure plasmaenvironments, as well as gas phase discharges, pulsed high voltagedischarges, etc. Denes, et al, use a first electrode comprising a firstconductive material immersed within the dense fluid medium and a secondelectrode comprising a second conductive material, also immersed withinthe dense fluid medium. Denes, et al then apply an electric potentialbetween the first and second electrodes to create a discharge zonebetween the electrodes to produce reactive species in the dense fluidmedium.

All of the constituents discussed above, if present, can be at leastpartially (or substantially completely) managed, controlled, adjusted,maximized, minimized, eliminated, etc., as a function of such speciesbeing helpful or harmful to the resultant nanoparticles and/ornanoparticle/solutions produced, and then may need to be controlled by avariety of different techniques (discussed in more detail later herein).As shown in FIG. 1 a, the adjustable plasma 4 contacts the actualsurface 2 of the liquid 3. In this embodiment of the invention, material(e.g., metal) from the electrode 1 may comprise a portion of theadjustable plasma 4 and may be caused, for example, to be “sputtered”onto and/or into the liquid (e.g., water). Accordingly, when metal(s)are used as the electrode(s) 1, elementary metal(s), metal ions, Lewisacids, Bronsted-Lowry acids, metal oxides, metal nitrides, metalhydrides, metal hydrates, metal carbides, and/or mixtures thereof etc.,can be found in the liquid (e.g., for at least a portion of theprocess), depending upon the particular set of operating conditionsassociated with the adjustable plasma 4 (as well as other operatingconditions).

Further, depending on, for example, electric, magnetic and/orelectromagnetic field strength, polarity, etc., in and around the liquid3, as well as the volume of liquid 3 present (e.g., a function of, forexample, the cross-sectional size and shape of the trough member 30and/or flow rate of the liquid 3) discussed in greater detail elsewhereherein), the physical and chemical construction of the electrode(s) 1and 5, atmosphere (naturally occurring or supplied), liquid 3composition, greater or lesser amounts of electrode(s) materials(s)(e.g., metal(s) or derivatives of metals) may be found in the liquid 3.Additional important information is disclosed in copending patentapplication entitled Methods for Controlling Crystal Growth,Crystallization, Structures and Phases in Materials and Systems; whichwas filed on Mar. 21, 2003, and was published by the World IntellectualProperty Organization under publication number WO 03/089692 on Oct. 30,2003 and the U.S. National Phase application, which was filed on Jun. 6,2005, and was published by the United States Patent and Trademark Officeunder publication number 20060037177 on Feb. 23, 2006 (the inventors ofeach being Bentley J. Blum, Juliana H. J. Brooks and Mark G. Mortenson).The subject matter of both applications is herein expressly incorporatedby reference. These published applications disclose (among other things)that the influence of, for example, electric fields, magnetic fields,electromagnetic energy, etc., have proven to be very important in theformation and/or control of various structures in a variety of solids,liquids, gases and/or plasmas. Such disclosed effects are also relevantin the embodiments disclosed herein. Further, the observation of extremevariations of, for example, pH in and around electrodes having apotential applied thereto (and current flow therethrough) also controlsreaction products and/or reaction rates. Thus, a complex set ofreactions are likely to be occurring at each electrode 1, 5 andelectrode assemblies or electrode sets (e.g., 1, 5; 1, 1; 5, 5; etc.).

In certain situations, the material(s) (e.g., metal(s), metal ion(s),metal composite(s) or constituents (e.g., Lewis acids, Bronsted-Lowryacids, etc.) and/or inorganics found in the liquid 3 (e.g., afterprocessing thereof) may have very desirable effects, in which caserelatively large amounts of such material(s) will be desirable; whereasin other cases, certain materials found in the liquid (e.g., undesirableby-products) may have undesirable effects, and thus minimal amounts ofsuch material(s) may be desired in the final product. Further, thestructure/composition of the liquid 3 per se may also be beneficially ornegatively affected by the processing conditions of the presentinvention. Accordingly, electrode composition can play an important rolein the ultimate material(s) (e.g., nanoparticles and/ornanoparticle/solutions) that are formed according to the embodimentsdisclosed herein. As discussed above herein, the atmosphere involvedwith the reactions occurring at the electrode(s) 1 (and 5) plays animportant role. However, electrode composition also plays an importantrole in that the electrodes 1 and 5 themselves can become part of, atleast partially, intermediate and/or final products formed.Alternatively, electrodes may have a substantial role in the finalproducts. In other words, the composition of the electrodes may be foundin large part in the final products of the invention or may compriseonly a small chemical part of products produced according to theembodiments disclosed herein. In this regard, when electrode(s) 1, 5 arefound to be somewhat reactive according to the process conditions of thevarious embodiments disclosed herein, it can be expected that ionsand/or physical particles (e.g., metal-based particles of single ormultiple crystals) from the electrodes can become part of a finalproduct. Such ions and/or physical components may be present as apredominant part of a particle in a final product, may exist for only aportion of the process, or may be part of a core in a core-shellarrangement present in a final product. Further, the core-shellarrangement need not include complete shells. For example, partialshells and/or surface irregularities or specific desirable surfaceshapes on a formed nanoparticle can have large influence on the ultimateperformance of such nanoparticles in their intended use. It should beclear to an artisan of ordinary skill that slight adjustments ofchemical composition, reactive atmospheres, power intensities, etc., cancause a variety of different chemical compounds (both semi-permanent andtransient) nanoparticles (and nanoparticle components) to be formed; aswell as different nanoparticle/solutions (e.g., including modifying thestructures of the liquid 3 (such as water) per se).

Still further, the electrode(s) 1 and 5 may be of similar chemicalcomposition or completely different chemical compositions and/or made bysimilar or completely different forming processes in order to achievevarious compositions of ions, compounds, and/or physical particles inliquid and/or structures of liquids per se and/or specific effects fromfinal resultant products. For example, it may be desirable thatelectrode pairs, shown in the various embodiments herein, be of the sameor substantially similar composition, or it may be desirable for theelectrode pairs, shown in the various embodiments herein, to be ofdifferent chemical composition(s). Different chemical compositions mayresult in, of course, different constituents being present for possiblereaction in the various plasma and/or electrochemical embodimentsdisclosed herein. Further, a single electrode 1 or 5 (or electrode pair)can be made of at least two different metals, such that components ofeach of the metals, under the process conditions of the disclosedembodiments, can interact with each other, as well as with otherconstituents in the plasma(s) 4 and or liquid(s) 3, fields, etc.,present in, for example, the plasma 4 and/or the liquid 3.

Further, the distance between the electrode(s) 1 and 5; or 1 and 1(e.g., see FIGS. 3 d, 4 d, 8 d and 9 d) or 5 and 5 (e.g., see FIGS. 3 c,4 c, 8 c and 9 c) is one important aspect of the invention. In general,the location of the smallest distance “y” between the closest portionsof the electrode(s) used in the present invention should be greater thanthe distance “x” in order to prevent an undesirable arc or formation ofan unwanted corona or plasma occurring between the electrode (e.g., theelectrode(s) 1 and the electrode(s) 5). Various electrode design(s),electrode location(s) and electrode interaction(s) are discussed in moredetail in the Examples section herein.

The power applied through the power source 10 may be any suitable powerwhich creates a desirable adjustable plasma 4 and desirable adjustableelectrochemical reaction under all of the process conditions of thepresent invention. In one preferred mode of the invention, analternating current from a step-up transformer (discussed in the “PowerSources” section and the “Examples” section) is utilized. In otherpreferred embodiments of the invention, polarity of an alternatingcurrent power source is modified by diode bridges to result in apositive electrode 1 and a negative electrode 5; as well as a positiveelectrode 5 and a negative electrode 1. In general, the combination ofelectrode(s) components 1 and 5, physical size and shape of theelectrode(s) 1 and 5, electrode manufacturing process, mass ofelectrodes 1 and/or 5, the distance “x” between the tip 9 of electrode 1above the surface 2 of the liquid 3, the composition of the gas betweenthe electrode tip 9 and the surface 2, the flow rate and/or flowdirection “F” of the liquid 3, compositions of the liquid 3,conductivity of the liquid 3, voltage, amperage, polarity of theelectrodes, etc., all contribute to the design, and thus powerrequirements (e.g., breakdown electric field or “E_(c)” of Equation 1)all influence the formation of a controlled or adjustable plasma 4between the surface 2 of the liquid 3 and the electrode tip 9.

In further reference to the configurations shown in FIGS. 1 a and 1 b,electrode holders 6 a and 6 b are capable of being lowered and raised(and thus the electrodes are capable of being lowered and raised) in andthrough an insulating member 8 (shown in cross-section). The embodimentshown here are male/female screw threads. However, the electrode holders6 a and 6 b can be configured in any suitable means which allows theelectrode holders 6 a and 6 b to be raised and/or lowered reliably. Suchmeans include pressure fits between the insulating member 8 and theelectrode holders 6 a and 6 b, notches, mechanical hanging means,movable annulus rings, etc. In other words, any means for reliablyfixing the height of the electrode holders 6 a and 6 b should beconsidered as being within the metes and bounds of the embodimentsdisclosed herein.

For example, FIG. 1 c shows another embodiment for raising and loweringthe electrodes 1, 5. In this embodiment, electrical insulating portions7 a and 7 b of each electrode are held in place by a pressure fitexisting between the friction mechanism 13 a, 13 b and 13 c, and theportions 7 a and 7 b. The friction mechanism 13 a, 13 b and 13 c couldbe made of, for example, spring steel, flexible rubber, etc., so long assufficient contact is maintained thereafter.

The portions 6 a and 6 b can be covered by, for example, additionalelectrical insulating portions 7 a and 7 b. The electrical insulatingportions 7 a and 7 b can be any suitable electrically insulatingmaterial (e.g., plastic, rubber, fibrous materials, etc.) which preventundesirable currents, voltage, arcing, etc., that could occur when anindividual interfaces with the electrode holders 6 a and 6 b (e.g.,attempts to adjust the height of the electrodes). Moreover, rather thanthe electrical insulating portion 7 a and 7 b simply being a cover overthe electrode holder 6 a and 6 b, such insulating portions 7 a and 7 bcan be substantially completely made of an electrical insulatingmaterial. In this regard, a longitudinal interface may exist between theelectrical insulating portions 7 a/7 b and the electrode holder 6 a/6 brespectively (e.g., the electrode holder 6 a/6 b may be made of acompletely different material than the insulating portion 7 a/7 b andmechanically or chemically (e.g., adhesively) attached thereto.

Likewise, the insulating member 8 can be made of any suitable materialwhich prevents undesirable electrical events (e.g., arcing, melting,etc.) from occurring, as well as any material which is structurally andenvironmentally suitable for practicing the present invention. Typicalmaterials include structural plastics such as polycarbonate plexiglass(poly(methyl methacrylate), polystyrene, acrylics, and the like. Certaincriteria for selecting structural plastics and the like include, but arenot limited to, the ability to maintain shape and/or rigidity, whileexperiencing the electrical, temperature and environmental conditions ofthe process. Preferred materials include acrylics, plexiglass, and otherpolymer materials of known chemical, electrical and electricalresistance as well as relatively high mechanical stiffness. In thisregard, desirable thicknesses for the member 8 are on the order of about1/16″-¾″ (1.6 mm-19.1 mm).

The power source 10 can be connected in any convenient electrical mannerto the electrodes 1 and 5. For example, wires 11 a and 11 b can belocated within at least a portion of the electrode holders 6 a, 6 b witha primary goal being achieving electrical connections between theportions 11 a, 11 b and thus the electrodes 1, 5. Specific details ofpreferred electrical connections are discussed elsewhere herein.

FIG. 2 a shows another schematic view of a preferred embodiment of theinvention, wherein an inventive control device 20 is connected to theelectrodes 1 and 5, such that the control device 20 remotely (e.g., uponcommand from another device) raises and/or lowers the electrodes 1, 5relative to the surface 2 of the liquid 3. The inventive control device20 is discussed in more detail later herein. In this preferredembodiment of the invention, the electrodes 1 and 5 can be, for example,remotely lowered and controlled, and can also be monitored andcontrolled by a suitable controller or computer (not shown in FIG. 2 a)containing a software program (discussed in detail later herein). Inthis regard, FIG. 2 b shows an electrode configuration similar to thatshown in FIG. 2 a, except that a Taylor cone “T” is utilized forelectrical connection between the electrode 5 and the effective surface2′ of the liquid 3. Accordingly, the embodiments shown in FIGS. 1 a, 1 band 1 c should be considered to be a manually controlled apparatus foruse with the teachings of the present invention, whereas the embodimentsshown in FIGS. 2 a and 2 b should be considered to include an automaticapparatus or assembly which can remotely raise and lower the electrodes1 and 5 in response to appropriate commands. Further, the FIG. 2 a andFIG. 2 b preferred embodiments of the invention can also employ computermonitoring and computer control of the distance “x” of the tips 9 of theelectrode(s) 1 (and tips 9′ of the electrodes 5) away from the surface 2(discussed in greater detail later herein). Thus, the appropriatecommands for raising and/or lowering the electrodes 1 and 5 can comefrom an individual operator and/or a suitable control device such as acontroller or a computer (not shown in FIG. 2 a).

FIG. 3 a corresponds in large part to FIGS. 2 a and 2 b, however, FIGS.3 b, 3 c and 3 d show various alternative electrode configurations thatcan be utilized in connection with certain preferred embodiments of theinvention. FIG. 3 b shows essentially a mirror image electrode assemblyfrom that electrode assembly shown in FIG. 3 a. In particular, as shownin FIG. 3 b, with regard to the direction “F” corresponding to the flowdirection of the liquid 3 in FIG. 3 b, the electrode 5 is the firstelectrode which communicates with the fluid 3 when flowing in thelongitudinal direction “F” and the electrode 1 subsequently contacts thefluid 3 already modified by the electrode 5. FIG. 3 c shows twoelectrodes 5 a and 5 b located within the fluid 3. This particularelectrode configuration corresponds to another preferred embodiment ofthe invention. In particular, any of the electrode configurations shownin FIGS. 3 a-3 d, can be used in combination with each other. Forexample, the electrode configuration (i.e., the electrode set) shown inFIG. 3 a can be the first electrode set or configuration that a liquid 3flowing in the direction “F” encounters. Thereafter, the liquid 3 couldencounter a second electrode set or configuration 3 a; or alternatively,the liquid 3 could encounter a second electrode set or configuration 3b; or, alternatively, the liquid 3 flowing in the direction “F” couldencounter a second electrode set like that shown in FIG. 3 c; or,alternatively, the liquid 3 flowing in the direction “F” could encountera second electrode set similar to that shown in FIG. 3 d. Alternatively,if the first electrode configuration or electrode set encountered by aliquid 3 flowing in the direction “F” is the electrode configurationshown in FIG. 3 a, a second electrode set or configuration could besimilar to that shown in FIG. 3 c and a third electrode set or electrodeconfiguration that a liquid 3 flowing in the direction “F” couldencounter could thereafter be any of the electrode configurations shownin FIGS. 3 a-3 d. Alternatively, a first electrode set or configurationthat a liquid 3 flowing in the direction “F” could encounter could bethat electrode configuration shown in FIG. 3 d; and thereafter a secondelectrode set or configuration that a liquid 3 flowing in the direction“F” could encounter could be that electrode configuration shown in FIG.3 c; and thereafter any of the electrode sets or configurations shown inFIGS. 3 a-3 d could comprise the configuration for a third set ofelectrodes. Still further, a first electrode configuration that a liquid3 flowing in the direction “F” may encounter could be the electrodeconfiguration shown in FIG. 3 a; and a second electrode configurationcould be an electrode configuration also shown in FIG. 3 a; andthereafter a plurality of electrode configurations similar to that shownin FIG. 3 c could be utilized. In another embodiment, all of theelectrode configurations could be similar to that of FIG. 3 a. In thisregard, a variety of electrode configurations (including number ofelectrode sets utilized) are possible and each electrode configurationresults in either very different resultant constituents in the liquid 3(e.g., nanoparticle or nanoparticle/solution mixtures) or only slightlydifferent constituents (e.g., nanoparticle/nanoparticle solutionmixtures) all of which may exhibit different properties (e.g., differentchemical properties, different reactive properties, different catalyticproperties, etc.). In order to determine the desired number of electrodesets and desired electrode configurations and more particularly adesirable sequence of electrode sets, many factors need to be consideredincluding all of those discussed herein such as electrode composition,plasma composition (and atmosphere composition) and intensity, powersource, electrode polarity, voltage, amperage, liquid flow rate, liquidcomposition, liquid conductivity, cross-section (and volume of fluidtreated), magnetic, electromagnetic and/or electric fields created inand around each of the electrodes in each electrode assembly, whetherany field intensifiers are included, additional desired processing steps(e.g., electromagnetic radiation treatment) the desired amount ofcertain constituents in an intermediate product and in the finalproduct, etc. Some specific examples of electrode assembly combinationsare included in the “Examples” section later herein. However, it shouldbe understood that the embodiments of the present invention allow aplethora of electrode combinations and numbers of electrode sets, any ofwhich can result in very desirable nanoparticles/solutions for differentspecific chemical, catalytic, biological and/or physical applications.

With regard to the adjustable plasmas 4 shown in FIGS. 3 a, 3 b and 3 d,the distance “x” (or in FIG. 3 d “xa” and “xb”) are one means forcontrolling certain aspects of the adjustable plasma 4. In this regard,if nothing else in FIG. 3 a, 3 b or 3 d was changed except for thedistance “x”, then different intensity adjustable plasmas 4 can beachieved. In other words, one adjustment means for adjusting plasma 4(e.g., the intensity) is adjusting the distance “x” between the tip 9 ofthe electrode 1 and the surface 2 of the fluid 3. Changing of suchdistance can be accomplished up to a maximum distance “x” where thecombined voltage and amperage are no longer are sufficient to cause abreakdown of the atmosphere between the tip 9 and the surface 2according to Equation 1. Accordingly, the maximum preferable distances“x” are just slightly within or below the range where “E_(c)” breakdownof the atmosphere begins, to occur. Alternatively, the minimum distances“x” are those distances where an adjustable plasma 4 forms in contrastto the other phenomena discussed earlier herein where a Taylor coneforms. In this regard, if the distance “x” becomes so small that theliquid 3 tends to wick or contact the tip 9 of the electrode 1, then novisually absorbable plasma will be formed. Accordingly, the minimum andmaximum distances “x” are a function of all of the factors discussedelsewhere herein including amount of power applied to the system,composition of the atmosphere, composition (e.g., electricalconductivity) of the liquid, etc. Further, intensity changes in theplasma(s) 4 may also result in certain species becoming active, relativeto other processing conditions. This may result in, for example,different spectral emissions as well as changes in amplitude of variousspectral lines in the plasma(s) 4. Certain preferred distances “x” for avariety of electrode configurations and compositions are discussed inthe “Examples” section later herein.

Still further, with regard to FIG. 3 d, the distances “xa” and “xb” canbe about the same or can be substantially different. In this regard, inone preferred embodiment of the invention, for a liquid 3 flowing in thedirection “F”, it is desirable that the adjustable plasma 4 a havedifferent properties than the adjustable plasma 4 b. In this regard, itis possible that different atmospheres can be provided so that thecomposition of the plasmas 4 a and 4 b are different from each other,and it is also possible that the height “xa” and “xb” are different fromeach other. In the case of differing heights, the intensity or powerassociated with each of the plasmas 4 a and 4 b can be different (e.g.,different voltages can be achieved). In this regard, because theelectrodes 1 a and 1 b are electrically connected, the total amount ofpower in the system will remain substantially constant, and the amountof power thus provided to one electrode 1 a or 1 b will increase at theexpense of the power decreasing in the other electrode 1 a or 1 b.Accordingly, this is another inventive embodiment for controllingconstituents and/or intensity and/or presence or absence of spectralpeaks in the plasmas 4 a and 4 b and thus adjusting their interactionswith the liquid 3 flowing in the direction “F”.

Likewise, a set of manually controllable electrode configurations areshown in FIGS. 4 a, 4 b, 4 c and 4 d which are shown in a partialcross-sectional view. Specifically, FIG. 4 a corresponds substantiallyto FIG. 1 a. Moreover, FIG. 4 b corresponds in electrode configurationto the electrode configuration shown in FIG. 3 b; FIG. 4 c correspondsto FIG. 3 c and FIG. 4 d corresponds to FIG. 3 d. In essence, the manualelectrode configurations shown in FIGS. 4 a-4 d can functionally resultin similar materials produced according to the inventive aspects of theinvention as those materials and compositions produced corresponding toremotely adjustable (e.g., remote-controlled) electrode configurationsshown in FIGS. 3 a-3 d. However, one or more operators will be requiredto adjust manually those electrode configurations. Still further, incertain embodiments, a combination of manually controlled and remotelycontrolled electrode(s) and/or electrode sets may be desirable.

FIGS. 5 a-5 e show perspective views of various desirable electrodeconfigurations for the electrode(s) 1 shown in the Figures herein. Theelectrode configurations shown in FIGS. 5 a-5 e are representative of anumber of different configurations that are useful in variousembodiments of the present invention. Criteria for appropriate electrodeselection for the electrode 1 include, but are not limited to thefollowing conditions: the need for a very well defined tip or point 9,composition of the electrode 1, mechanical limitations encountered whenforming the compositions comprising the electrode 1 into various shapes,shape making capabilities associated with forging techniques, wiredrawing and/or casting processes utilized to make shapes, convenience,etc. In this regard, a small mass of material comprising the electrodes1 shown in, for example, FIGS. 1-4 may, upon creation of the adjustableplasmas 4 according to the present invention, rise to operationtemperatures where the size and or shape of the electrode(s) 1 can beadversely affected. The use of the phrase “small mass” should beunderstood as being a relative description of an amount of material usedin an electrode 1, which will vary in amount as a function ofcomposition, forming means, process conditions experienced in the troughmember 30, etc. For example, if an electrode 1, comprises silver, and isshaped similar to the electrode shown in FIG. 5 a, in certain preferredembodiments shown in the Examples section herein, its mass would beabout 0.5 grams-8 grams with a preferred mass of about 1 gram-3 grams;whereas if an electrode 1, comprises copper, and is shaped similar tothe electrode shown in FIG. 5 a, in certain preferred embodiments shownin the Examples section herein, its mass would be about 0.5 grams-6grams with a preferred mass of about 1 gram-3 grams; whereas if anelectrode 1, comprises zinc, and is shaped similar to the electrodeshown in FIG. 5 a, in certain preferred embodiments shown in theExamples section herein, its mass would be about 0.5 grams-4 grams witha preferred mass of about 1 gram-3 grams; whereas if the electrode 1comprises gold and is shaped similar to the electrode shown in FIG. 5 e,its mass would be about 1.5 grams-20 grams with a preferred mass ofabout 5 grams-10 grams. In this regard, for example, when the electrode1 comprises a relatively small mass, then certain power limitations maybe associated with utilizing a small mass electrode 1. In this regard,if a large amount of power is applied to a relatively small mass andsuch power results in the creation of an adjustable plasma 4, then alarge amount of thermal energy can be concentrated in the small masselectrode 1. If the small mass electrode 1 has a very high meltingpoint, then such electrode may be capable of functioning as an electrode1 in the present invention. However, if the electrode 1 is made of acomposition which has a relatively low melting point (e.g., such assilver, aluminum, or the like) then under some (but not all) embodimentsof the invention, the thermal energy transferred to the small masselectrode 1 could cause one or more undesirable effects includingmelting, cracking, or disintegration of the small mass electrode 1.Accordingly, one choice for utilizing lower melting point metals is touse larger masses of such metals so that thermal energy can bedissipated throughout such larger mass. Alternatively, if a small masselectrode 1 with low melting point is desired, then some type of coolingmeans could be required. Such cooling means include, for example, simplefans blowing ambient or applied atmosphere past the electrode 1, orother such means as appropriate. However, one potential undesirableaspect for providing a cooling fan juxtaposed a small mass electrode 1is that the atmosphere involved with forming the adjustable plasma 4could be adversely affected. For example, the plasma could be found tomove or gyrate undesirably if, for example, the atmosphere flow aroundor between the tip 9 and the surface 2 of the liquid 3 was vigorous.Accordingly, the composition of (e.g., the material comprising) theelectrode(s) 1 may affect possible suitable electrode physical shape(s)due to, for example, melting points, pressure sensitivities,environmental reactions (e.g., the local environment of the adjustableplasma 4 could cause chemical, mechanical and/or electrochemical erosionof the electrode(s)), etc.

Moreover, it should be understood that in alternative preferredembodiments of the invention, well defined sharp points for the tip 9are not always required. In this regard, the electrode 1 shown in FIG. 5e (which is a perspective drawing) comprises a rounded point. It shouldbe noted that partially rounded or arc-shaped electrodes can alsofunction as the electrode 1 because often times the adjustable plasma 4,can be positioned or be located along various points of the electrode 1shown in FIG. 5 e. In this regard, FIG. 6 shows a variety of points“a-g” which correspond to initiating points 9 for the plasmas 4 a-4 gwhich occur between the electrode 1 and the surface 2 of the liquid 3.For example, in practicing certain preferred embodiments of theinvention, the precise location of the adjustable plasma 4 will vary asa function of time. Specifically, a first plasma 4 d may be formed atthe point d on the tip 9 of the electrode 1. Thereafter, the exactlocation of the plasma contact point on the tip 9 may change to, forexample, any of the other points 4 a-4 g. It should be noted that theschematic shown in FIG. 6 is greatly enlarged relative to the actualarrangement in the inventive embodiments, in order to make the pointthat the tip 9 on the electrode 1 may permit a variety of precise pointsa-g as being the initiating or contact point on tip 9 on the electrode1. Essentially, the location of the adjustable plasma 4 can vary inposition as a function of time and can be governed by electric breakdownof the atmosphere (according to Equation 1 herein) located between theelectrode 1 and the surface 2 of the liquid 3. Further, while theplasmas 4 a-4 g are represented as being cone-shaped, it should beunderstood that the plasmas 4, formed in connection with any of theelectrodes 1, shown in FIGS. 5 a-5 e, may comprise shapes other thancones for a portion of, or substantially all of, the process conditions.For example, shapes best described as lightning bolts or glowingcylinders can also be present. Further, the colors emitted by suchplasmas 4 (e.g., in the visible spectrum) can vary wildly from reddishin color, bluish in color, yellow in color, orangish in color, violet incolor, white in color, etc., which colors are a function of atmospherepresent, voltage, amperage, electrode composition, liquid composition,etc.

Accordingly, it should be understood that a variety of sizes and shapescorresponding to electrode 1 can be utilized in accordance with theteachings of the present invention. Still further, it should be notedthat the tips 9 of the electrodes 1 shown in various figures herein maybe shown as a relatively sharp point or a relatively blunt end. Unlessspecific aspects of these electrode tips are discussed in greatercontextual detail, the actual shape of the electrode tip(s) shown in theFigures should not be given great significance.

FIG. 7 a shows a cross-sectional perspective view of the electrodeconfiguration corresponding to that shown in FIG. 2 a (and FIG. 3 a)contained within a trough member 30. This trough member 30 has a liquid3 supplied into it from the back side 31 of FIG. 7 a and the flowdirection “F” is out of the page toward the reader and toward thecross-sectional area identified as 32. The trough member 30 is shownhere as a unitary of piece of one material, but could be made from aplurality of materials fitted together and, for example, fixed (e.g.,glued, mechanically attached, etc.) by any acceptable means forattaching materials to each other. Further, the trough member 30 shownhere is of a rectangular or square cross-sectional shape, but maycomprise a variety of different cross-sectional shapes. Further, thetrough member 30 does not necessarily need to be made of a singlecross-sectional shape, but in another preferred embodiment herein,comprises a plurality of different cross-sectional shapes. In a firstpreferred embodiment the cross-sectional shape is roughly the samethroughout the longitudinal dimension of the trough member 30 but thesize dimensions of the cross-sectional shape change in coordination withdifferent plasma and/or electrochemical reactions. Further, more thantwo cross-sectional shapes can be utilized in a unitary trough member30. The advantages of the different cross-sectional shapes include, butare not limited to, different power, electric field, magnetic field,electromagnetic interactions, electrochemical, effects, differentchemical reactions in different portions, etc., which are capable ofbeing achieved in different longitudinal portions of the same unitarytrough member 30. Still further, some of the different cross-sectionalshapes can be utilized in conjunction with, for example, differentatmospheres being provided locally or globally such that at least one ofthe adjustable plasma(s) 4 and/or at least one of the electrochemicalreactions occurring at the electrode(s) 5 are a function of differentpossible atmospheres and/or atmospheric concentrations of constituentstherein. Further, the amount or intensity of applied and/or createdfluids can be enhanced by, for example, cross-sectional shape, as wellas by providing, for example, various field concentrators at, near,adjacent to or juxtaposed against various electrode sets or electrodeconfigurations to enhance or diminish one or more reactions occurringthere. Accordingly, the cross-sectional shape of the trough member 30can influence both liquid 3 interactions with the electrode(s) as wellas adjustable plasma 4 interactions with the liquid 3.

Still further, it should be understood that a trough member need not beonly linear or “I-shaped”, but rather, may be shaped like a “Y” or likea “Ψ”, each portion of which may have similar or dissimilarcross-sections. One reason for a “Y” or “Ψ”-shaped trough member 30 isthat two different sets of processing conditions can exist in the twoupper portions of the “Y”-shaped trough member 30. Further, a third setof processing conditions can exist in the bottom portion of the“Y”-shaped trough member 30. Thus, two different fluids 3, of differentcompositions and/or different reactants, could be brought together intothe bottom portion of the “Y”-shaped trough member 30 and processedtogether to from a large variety of final products.

FIG. 11 e shows an alternative configuration for the trough member 30.Specifically, the trough member 30 is shown in perspective view and is“Y-shaped”. Specifically, the trough member 30 comprises top portions 30a and 30 b and a bottom portion 30 o. Likewise, inlets 31 a and 31 b areprovided along with outlet 32. A portion 30 d corresponds to the pointwhere 30 a and 30 b meet 30 o.

FIG. 11 f shows the same “Y-shaped” trough member shown in FIG. 11 e,except that the portion 30 d of FIG. 11 e is now shown as a mixingsection 30 d′. In this regard, certain constituents manufactured orproduced in the liquid 3 in one or all of, for example, the portions 30a, 30 b and/or 30 c, may be desirable to be mixed together at the point30 d (or 30 d′). Such mixing may occur naturally at the intersection 30d shown in FIG. 11 e (i.e., no specific or special section 30 d′ may beneeded), or may be more specifically controlled at the portion 30 d′. Itshould be understood that the portion 30 d′ could be shaped in anyeffective shape, such as square, circular, rectangular, etc., and be ofthe same or different depth relative to other portions of the troughmember 30. In this regard, the area 30 d could be a mixing zone orsubsequent reaction zone.

FIGS. 11 g and 11 h show a “Ψ-shaped” trough member 30. Specifically, anew portion 30 c has been added. Other features of FIGS. 11 g and 11 hare similar to those features shown in 11 e and 11 f.

It should be understood that a variety of different shapes can exist forthe trough member 30, any one of which can produce desirable results.

Again with regard to FIG. 7 a, the flow direction of the liquid 3 is outof the page toward the reader and the liquid 3 flows past each of theelectrode(s) 1 and 5, sequentially, which are, in this embodiment,located substantially in line with each other relative to thelongitudinal flow direction “F” of the liquid 3 within the trough member30 (e.g., their arrangement is parallel to each other and thelongitudinal dimensions of the trough member 30). This causes the liquid3 to first experience an adjustable plasma 4 interaction with the liquid3 (e.g., a conditioning reaction) and subsequently then the conditionedliquid 3 can thereafter interact with the electrode 5. As discussedearlier herein, a variety of constituents can be expected to be presentin the adjustable plasma 4 and at least a portion of such constituentsor components (e.g., chemical, physical and/or fluid components) willinteract with at least of the portion of the liquid 3 and change theliquid 3. Accordingly, subsequent reactions (e.g., electrochemical) canoccur at electrode(s) 5 after such components or constituents oralternative liquid structure(s) have been caused to be present in theliquid 3. Thus, it should be apparent from the disclosure of the variousembodiments herein, that the type, amount and activity of constituentsor components in the adjustable plasma 4 are a function of a variety ofconditions associated with practicing the preferred embodiments of thepresent invention. Such constituents (whether transient or semipermanent), once present and/or having at least, partially modified theliquid 3, can favorably influence subsequent reactions along thelongitudinal direction of the trough member 30 as the liquid 3 flows inthe direction “F” therethrough. By adjusting the types of reactions(e.g., electrode assemblies and reactions associated therewith) andsequentially providing additional similar or different electrode sets orassemblies (such as those shown in FIGS. 3 a-3 d) a variety ofcompounds, nanoparticles and nanoparticle/solution(s) can be achieved.For example, nanoparticles may experience growth (e.g., apparent oractual) within the liquid 3 as constituents within the liquid 3 pass byand interact with various electrode sets (e.g., 5, 5) along thelongitudinal length of the trough member 30 (discussed in greater detailin the Examples section). Such growth, observed at, for example,electrode sets 5, 5, seems to be greatly accelerated when the liquid 3has previously been contacted with an electrode set 1, 5 and/or 1, 1and/or 5, 1. Depending on the particular final uses of the liquid 3produced according to the invention, certain nanoparticles, someconstituents in the liquid 3, etc., could be considered to be verydesirable; whereas other constituents could be considered to beundesirable. However, due to the versatility of the electrode design,number of electrode sets, electrode set configuration, fluidcomposition, processing conditions at each electrode in each electrodeassembly or set, sequencing of different electrode assemblies or setsalong the longitudinal direction of the trough member 30, shape of thetrough member 30, cross-sectional size and shape of the trough member30, all such conditions can contribute to more or less of desirable orundesirable constituents or components (transient or semi-permanent)present in the liquid 3 and/or differing structures of the liquid per seduring at least a portion of the processes disclosed herein.

FIG. 7 b shows a cross-sectional perspective view of the electrodeconfiguration shown in FIG. 2 a (as well as in FIG. 3 a), however, theseelectrodes 1 and 5 are rotated on the page 90 degrees relative to theelectrodes 1 and 5 shown in FIGS. 2 a and 3 a. In this embodiment of theinvention, the liquid 3 contacts the adjustable plasma 4 generatedbetween the electrode 1 and the surface 2 of the liquid 3, and theelectrode 5 at substantially the same point along the longitudinal flowdirection “F” (i.e., out of the page) of the trough member 30. Thedirection of liquid 3 flow is longitudinally along the trough member 30and is out of the paper toward the reader, as in FIG. 7 a. Accordingly,as discussed immediately above herein, it becomes clear that theelectrode assembly shown in FIG. 7 b can be utilized with one or more ofthe electrode assemblies or sets discussed above herein as well as laterherein. For example, one use for the assembly shown in FIG. 7 b is thatwhen the constituents created in the adjustable plasma 4 (or resultantproducts in the liquid 3) flow downstream from the contact point withthe surface 2 of the liquid 3, a variety of subsequent processing stepscan occur. For example, the distance “y” between the electrode 1 and theelectrode 5 (as shown, for example, in FIG. 7 b) is limited to certainminimum distances as well as certain maximum distances. The minimumdistance “y” is that distance where the distance slightly exceeds theelectric breakdown “E_(c)” of the atmosphere provided between theclosest points between the electrodes 1 and 5. Whereas the maximumdistance “y” corresponds to the distance at a maximum which at leastsome conductivity of the fluid permits there to be an electricalconnection from the power source 10 into and through each of theelectrode(s) 1 and 5 as well as through the liquid 3. The maximumdistance “y” will vary as a function of, for example, constituentswithin the liquid 3 (e.g., conductivity of the liquid 3). Accordingly,some of those highly energized constituents comprising the adjustableplasma 4 could be very reactive and could create compounds (reactive orotherwise) within the liquid 3 and a subsequent processing step could beenhanced by the presence of such constituents or such very reactivecomponents or constituents could become less reactive as a function of,for example, time. Moreover, certain desirable or undesirable reactionscould be minimized or maximized by locations and/or processingconditions associated with additional electrode sets downstream fromthat electrode set shown in, for example, FIG. 7 b.

FIG. 8 a shows a cross-sectional perspective view of the same embodimentshown in FIG. 7 a. In this embodiment, as in the embodiment shown inFIG. 7 a, the fluid 3 firsts interacts with the adjustable plasma 4created between the electrode 1 and the surface 2 of the liquid 3.Thereafter the plasma influenced or conditioned fluid 3, having beenchanged (e.g., conditioned, or modified or prepared) by the adjustableplasma 4, thereafter communicates with the electrode 5 thus permittingvarious electrochemical reactions to occur, such reactions beinginfluenced by the state (e.g., chemical composition, physical or crystalstructure, excited state(s), etc., of the fluid 3 (and constituents orcomponents in the fluid 3)). An alternative embodiment is shown in FIG.8 b. This embodiment essentially corresponds in general to thoseembodiments shown in FIGS. 3 b and 4 b. In this embodiment, the fluid 3first communicates with the electrode 5, and thereafter the fluid 3communicates with the adjustable plasma 4 created between the electrode1 and the surface 2 of the liquid 3.

FIG. 8 c shows a cross-sectional perspective view of two electrodes 5 aand 5 b (corresponding to the embodiments shown in FIGS. 3 c and 4 c)wherein the longitudinal flow direction “F” of the fluid 3 contacts thefirst electrode 5 a and thereafter contacts the second electrode 5 b inthe direction “F” of fluid flow.

Likewise, FIG. 8 d is a cross-sectional perspective view and correspondsto the embodiments shown in FIGS. 3 d and 4 d. In this embodiment, thefluid 3 communicates with a first adjustable plasma 4 a created by afirst electrode 1 a and thereafter communicates with a second adjustableplasma 4 b created between a second electrode 1 b and the surface 2 ofthe fluid 3.

Accordingly, it should be clear from the disclosed embodiments that thevarious electrode configurations or sets shown in FIGS. 8 a-8 d can beused alone or in combination with each other in a variety of differentconfigurations. A number of factors direct choices for which electrodeconfigurations are best to be used to achieve various desirable results.As well, the number of such electrode configurations and the location ofsuch electrode configurations relative to each other all influenceresultant constituents within the liquid 3, nanoparticles and/ornanoparticle/liquid solutions resulting therefrom. Some specificexamples of electrode configuration dependency are included in the“Examples” section herein. However, it should be apparent to the readera variety of differing products and desirable set-ups are possibleaccording to the teachings (both expressly and inherently) presentherein, which differing set-ups can result in very different products(discussed further in the “Examples” section herein).

FIG. 9 a shows a cross-sectional perspective view and corresponds to theelectrode configuration shown in FIG. 7 b (and generally to theelectrode configuration shown in FIGS. 3 a and 4 a but is rotated 90degrees relative thereto). All of the electrode configurations shown inFIGS. 9 a-9 d are situated such that the electrode pairs shown arelocated substantially at the same longitudinal point along the troughmember 30, as in FIG. 7 b.

Likewise, FIG. 9 b corresponds generally to the electrode configurationshown in FIGS. 3 b and 4 b, and is rotated 90 degrees relative to theconfiguration shown in FIG. 8 b.

FIG. 9 c shows an electrode configuration corresponding generally toFIGS. 3 c and 4 c, and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8 c.

FIG. 9 d shows an electrode configuration corresponding generally toFIGS. 3 d and 4 d and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8 d.

As discussed herein, the electrode configurations or sets showngenerally in FIGS. 7, 8 and 9, all can create different results (e.g.,different sizes, shapes, amounts, compounds, constituents, functioningof nanoparticles present in a liquid, different liquid structures,different pH's, etc.) as a function of their orientation and positionrelative to the fluid flow direction “F” and relative to theirpositioning in the trough member 30, relative to each other. Further,the electrode number, compositions, size, specific shapes, voltagesapplied, amperages applied, fields created, distance between electrodesin each electrode set, distance between electrode sets, etc., can allinfluence the properties of the liquid 3 as it flows past theseelectrodes and hence resultant properties of the materials (e.g., theconstituents in the fluid 3, the nanoparticles and/or thenanoparticle/solution) produced therefrom. Additionally, theliquid-containing trough member 30, in some preferred embodiments,contains a plurality of the electrode combinations shown in FIGS. 7, 8and 9. These electrode assemblies may be all the same or may be acombination of various different electrode configurations. Moreover, theelectrode configurations may sequentially communicate with the fluid “F”or may simultaneously, or in parallel communicate with the fluid “F”.Different exemplary electrode configurations are shown in additionalfigures later herein and are discussed in greater detail later herein(e.g., in the “Examples” section) in conjunction with differentconstituents produced in the liquid 3, nanoparticles and/or differentnanoparticle/solutions produced therefrom.

FIG. 10 a shows a cross-sectional view of the liquid containing troughmember 30 shown in FIGS. 7, 8 and 9. This trough member 30 has across-section corresponding to that of a rectangle or a square and theelectrodes (not shown in FIG. 10 a) can be suitably positioned therein.

Likewise, several additional alternative cross-sectional embodiments forthe liquid-containing trough member 30 are shown in FIGS. 10 b, 10 c, 10d and 10 e. The distance “S” and “S′” for the preferred embodimentsshown in each of FIGS. 10 a-10 e measures, for example, between about 1″and about 3″ (about 2.5 cm-7.6 cm). The distance “M” ranges from about2″ to about 4″ (about 5 cm⁻¹⁰ cm). The distance “R” ranges from about1/16″-½″ to about 3″ (about 1.6 mm-13 mm to about 76 mm). All of theseembodiments (as well as additional configurations that representalternative embodiments are within the metes and bounds of thisinventive disclosure) can be utilized in combination with the otherinventive aspects of the invention. It should be noted that the amountof liquid 3 contained within each of the liquid containing troughmembers 30 is a function not only of the depth “d”, but also a functionof the actual cross-section. Briefly, the amount or volume of liquid 3present in and around the electrode(s) 1 and 5 can influence one or moreeffect(s) (e.g., fluid or concentration effects including fieldconcentration effects) of the adjustable plasma 4 upon the liquid 3 aswell as one or more chemical or electrochemical interaction(s) of theelectrode 5 with the liquid 3. These effects include not only adjustableplasma 4 conditioning effects (e.g., interactions of the plasma electricand magnetic fields, interactions of the electromagnetic radiation ofthe plasma, creation of various chemical species (e.g., Lewis acids,Bronsted-Lowry acids, etc.) within the liquid, pH changes, etc.) uponthe liquid 3, but also the concentration or interaction of theadjustable plasma 4 with the liquid 3 and electrochemical interactionsof the electrode 5 with the liquid 3. Different effects are possible dueto, for example, the actual volume of liquid present around alongitudinal portion of each electrode assembly 1 and/or 5. In otherwords, for a given length along the longitudinal direction of the troughmember 30, different amounts or volume of liquid 3 will be present as afunction of cross-sectional shape. As a specific example, reference ismade to FIGS. 10 a and 10 c. In the case of FIG. 10 a, the rectangularshape shown therein has a top portion about the same distance apart asthe top portion shown in FIG. 10 c. However, the amount of fluid alongthe same given longitudinal amount (i.e., into the page) will besignificantly different in each of FIGS. 10 a and 10 c.

Similarly, the influence of many aspects of the electrode 5 on theliquid 3 (e.g., electrochemical interactions) is also, at leastpartially, a function of the amount of fluid juxtaposed to theelectrode(s) 5, as discussed immediately above herein.

Further, electric and magnetic field concentrations can alsosignificantly affect the interaction of the plasma 4 with the liquid 3,as well as affect the interactions of the electrode(s) 5 with the liquid3. For example, without wishing to be bound by any particular theory orexplanation, when the liquid 3 comprises water, a variety of electricfield, magnetic field and/or electromagnetic field influences can occur.Specifically, water is a known dipolar molecule which can be at leastpartially aligned by an electric field. Having partial alignment ofwater molecules with an electric field can, for example, causepreviously existing hydrogen bonding and bonding angles to be orientedat an angle different than prior to electric field exposure, causedifferent vibrational activity, or such bonds may actually be broken.Such changing in water structure can result in the water having adifferent (e.g., higher) reactivity. Further, the presence of electricand magnetic fields can have opposite effects on ordering or structuringof water and/or nanoparticles present in the water. It is possible thatunstructured or small structured water having relatively fewer hydrogenbonds relative to, for example, very structured water, can result in amore reactive (e.g., chemically more reactive) environment. This is incontrast to open or higher hydrogen-bonded networks which can slowreactions due to, for example, increased viscosity, reduceddiffusivities and a smaller activity of water molecules. Accordingly,factors which apparently reduce hydrogen bonding and hydrogen bondstrength (e.g, electric fields) and/or increase vibrational activity,can encourage reactivity and kinetics of various reactions.

Further, electromagnetic radiation can also have direct and indirecteffects on water and it is possible that the electromagnetic radiationper se (e.g., that radiation emitted from the plasma 4), rather than theindividual electric or magnetic fields alone can have such effects, asdisclosed in the aforementioned published patent application entitledMethods for Controlling Crystal Growth, Crystallization, Structures andPhases in Materials and Systems which has been incorporated by referenceherein. Different spectra associated with different plasmas 4 arediscussed in the “Examples” section herein.

Further, by passing an electric current through the electrode(s) 1and/or 5 disclosed herein, the voltages present on, for example, theelectrode(s) 5 can have an orientation effect (i.e., temporary,semi-permanent or longer) on the water molecules. The presence of otherconstituents (i.e., charged species) in the water may enhance suchorientation effects. Such orientation effects may cause, for example,hydrogen bond breakage and localized density changes (i.e., decreases).Further, electric fields are also known to lower the dielectric constantof water due to the changing (e.g., reduction of) the hydrogen bondingnetwork. Such changing of networks should change the solubilityproperties of water and may assist in the concentration or dissolutionof a variety of gases and/or constituents or reactive species in theliquid 3 (e.g., water) within the trough member 30. Still further, it ispossible that the changing or breaking of hydrogen bonds fromapplication of electromagnetic radiation (and/or electric and magneticfields) can perturb gas/liquid interfaces and result in more reactivespecies. Still further, changes in hydrogen bonding can affect carbondioxide hydration resulting in, among other things, pH changes. Thus,when localized pH changes occur around, for example, at least one ormore of the electrode(s) 5 (or electrode(s) 1), many of the possiblereactants (discussed elsewhere herein) will react differently withthemselves and/or the atmosphere and/or the adjustable plasma(s) 4 aswell as the electrode(s) 1 and/or 5, per se. The presence of Lewis acidsand/or Bronsted-Lowry acids, can also greatly influence reactions.

Further, a trough member 30 may comprise more than one cross-sectionalshapes along its entire longitudinal length. The incorporation ofmultiple cross-sectional shapes along the longitudinal length of atrough member 30 can result in, for example, a varying field orconcentration or reaction effects being produced by the inventiveembodiments disclosed herein. Additionally, various modifications can beadded at points along the longitudinal length of the trough member 30which can enhance and/or diminish various of the field effects discussedabove herein. In this regard, compositions of materials in and/or aroundthe trough (e.g., metals located outside or within at least a portion ofthe trough member 30) can act as concentrators or enhancers of variousof the fields present in and around the electrode(s) 1 and/or 5.Additionally, applications of externally-applied fields (e.g., electric,magnetic, electromagnetic, etc.) and/or the placement of certainreactive materials within the trough member 30 (e.g., at least partiallycontacting a portion of the liquid 3 flowing thereby) can also resultin: (1) a gathering, collecting or filtering of undesirable species; or(2) placement of desirable species onto, for example, at least a portionof an outer surface of nanoparticles already formed upstream therefrom.Further, it should be understood that a trough member 30 may not belinear or “I-shaped”, but rather may be “Y-shaped” or “Ψ-shaped”, witheach portion of the “Y” or “Ψ” having a different (or similar)cross-section. One reason for a “Y” or “Ψ-shaped” trough member 30 isthat two (or more) different sets of processing conditions can exist inthe two (or more) upper portions of the “Y-shaped” or “Ψ-shaped” troughmember 30. Further, another additional set of processing conditions canexist in the bottom portion of the “Y-shaped” trough member 30. Thus,different fluids 3, of different compositions and/or differentreactants, could be brought together into the bottom portion of the“Y-shaped” trough member 30 and processed together to from a largevariety of final products.

FIG. 11 a shows a perspective view of one embodiment of substantiallyall of the trough member 30 shown in FIG. 10 b including an inletportion or inlet end 31 and an outlet portion or outlet end 32. The flowdirection “F” discussed in other figures herein corresponds to a liquidentering at or near the end 31 (e.g., utilizing an appropriate means fordelivering fluid into the trough member 30 at or near the inlet portion31) and exiting the trough member 30 through the outlet end 32.Additionally, while a single inlet end 31 is shown in FIG. 11 a,multiple inlet(s) 31 could be present near that shown in FIG. 11 a, orcould be located at various positions along the longitudinal length ofthe trough member 30 (e.g., immediately upstream from one or more of theelectrode sets positioned along the trough member 30). Thus, theplurality of inlet(s) 31 can permit the introduction of more than oneliquid 3 at a first longitudinal end 31 thereof; or the introduction ofmultiple liquids 3 at the longitudinal end 31; and/or the introductionof different liquids 3 at different positions along the longitudinallength of the trough member 30.

FIG. 11 b shows the trough member 30 of FIG. 11 a containing threecontrol devices 20 removably attached to a top portion of the troughmember 30. The interaction and operations of the control devices 20containing the electrodes 1 and/or 5 are discussed in greater detaillater herein.

FIG. 11 c shows a perspective view of the trough member 30 incorporatingan atmosphere control device cover 35′. The atmosphere control device orcover 35′ has attached thereto a plurality of control devices 20 (inFIG. 11 c, three control devices 20 a, 20 b and 20 c are shown)containing electrode(s) 1 and/or 5. The cover 35′ is intended to providethe ability to control the atmosphere within and/or along a substantialportion of (e.g., greater than 50% of) the longitudinal direction of thetrough member 30, such that any adjustable plasma(s) 4 created at anyelectrode(s) 1 can be a function of voltage, current, current density,etc., as well as any controlled atmosphere provided. The atmospherecontrol device 35′ can be constructed such that one or more electrodesets can be contained within. For example, a localized atmosphere can becreated between the end portions 39 a and 39 b along substantially allor a portion of the longitudinal length of the trough member 30 and atop portion of the atmosphere control device 35′. An atmosphere can becaused to flow into at least one inlet port (not shown) incorporatedinto the atmosphere control device 35′ and can exit through at least oneoutlet port (not shown), or be permitted to enter/exit along or near,for example, the portions 39 a and 39 b. In this regard, so long as apositive pressure is provided to an interior portion of the atmospherecontrol device 35′ (i.e., positive relative to an external atmosphere)then any such gas can be caused to bubble out around the portions 39 aand/or 39 b. Further, depending on, for example, if one portion of 39 aor 39 b is higher relative to the other, an internal atmosphere may alsobe appropriately controlled. A variety of atmospheres suitable for usewithin the atmosphere control device 35′ include conventionally regardednon-reactive atmospheres like noble gases (e.g., argon or helium) orconventionally regarded reactive atmospheres like, for example, oxygen,nitrogen, ozone, controlled air, etc. The precise composition of theatmosphere within the atmosphere control device 35′ is a function ofdesired processing techniques and/or desired constituents to be presentin the plasma 4 and/or the liquid 3, desired nanoparticles/compositenanoparticles and/or desired nanoparticles/solutions.

FIG. 11 d shows the apparatus of FIG. 11 c including an additionalsupport means 34 for supporting the trough member 30 (e.g., on anexterior portion thereof), as well as supporting (at least partially)the control devices 20 (not shown in this FIG. 11 c). It should beunderstood that various details can be changed regarding, for example,the cross-sectional shapes shown for the trough member 30, atmospherecontrol(s) (e.g., the atmosphere control device 35′) and externalsupport means (e.g., the support means 34) all of which should beconsidered to be within the metes and bounds of this inventivedisclosure. The material(s) comprising the additional support means 34for supporting the trough member 30 can be any material which isconvenient, structurally sound and non-reactive under the processconditions practiced for the present inventive disclosure. Acceptablematerials include polyvinyls, acrylics, plexiglass, structural plastics,nylons, teflons, etc., as discussed elsewhere herein.

FIG. 11 e shows an alternative configuration for the trough member 30.Specifically, the trough member 30 is shown in perspective view and is“Y-shaped”. Specifically, the trough member 30 comprises top portions 30a and 30 b and a bottom portion 30 o. Likewise, inlets 31 a and 31 b areprovided along with outlet 32. A portion 30 d corresponds to the pointwhere 30 a and 30 b meet 30 o.

FIG. 11 f shows the same “Y-shaped” trough member shown in FIG. 11 e,except that the portion 30 d of FIG. 11 e is now shown as a mixingsection 30 d′. In this regard, certain constituents manufactured orproduced in the liquid 3 in one or all of, for example, the portions 30a, 30 b and/or 30 c, may be desirable to be mixed together at the point30 d (or 30 d′). Such mixing may occur naturally at the intersection 30d shown in FIG. 11 e (i.e., no specific or special section 30 d′ may beneeded), or may be more specifically controlled at the portion 30 d′. Itshould be understood that the portion 30 d′ could be shaped in anyeffective shape, such as square, circular, rectangular, etc., and be ofthe same or different depth relative to other portions of the troughmember 30. In this regard, the area 30 d could be a mixing zone orsubsequent reaction zone.

FIGS. 11 g and 11 h show a “Ψ-shaped” trough member 30. Specifically, anew portion 30 c has been added. Other features of FIGS. 11 g and 11 hare similar to those features shown in 11 e and 11 f.

It should be understood that a variety of different shapes can exist forthe trough member 30, any one of which can produce desirable results.

FIG. 12 a shows a perspective view of a local atmosphere controlapparatus 35 which functions as a means for controlling a localatmosphere around at least one electrode set 1 and/or 5 so that variouslocalized gases can be utilized to, for example, control and/or effectcertain parameters of the adjustable plasma 4 between electrode 1 andsurface 2 of the liquid 3, as well as influence certain constituentswithin the liquid 3 and/or adjustable electrochemical reactions atand/or around the electrode(s) 5. The through-holes 36 and 37 shown inthe atmosphere control apparatus 35 are provided to permit externalcommunication in and through a portion of the apparatus 35. Inparticular, the hole or inlet 37 is provided as an inlet connection forany gaseous species to be introduced to the inside of the apparatus 35.The hole 36 is provided as a communication port for the electrodes 1and/or 5 extending therethrough which electrodes are connected to, forexample, the control device 20 above the apparatus 35. Gasses introducedthrough the inlet 37 can simply be provided at a positive pressurerelative to the local external atmosphere and may be allowed to escapeby any suitable means or pathway including, but not limited to, bubblingout around the portions 39 a and/or 39 b of the apparatus 35, when suchportions are caused, for example, to be at least partially submergedbeneath the surface 2 of the liquid 3. Generally, the portions 39 a and39 b can break the surface 2 of the liquid 3 effectively causing thesurface 2 to act as part of the seal to form a localized atmospherearound electrode sets 1 and/or 5. When a positive pressure of a desiredgas enters through the inlet port 37, small bubbles can be caused tobubble past, for example, the portions 39 a and/or 39 b. Additionally,the precise location of the inlet 37 can also be a function of the gasflowing therethrough. Specifically, if a gas providing at least aportion of a localized atmosphere is heavier than air, then an inletportion above the surface 2 of the liquid 3 should be adequate. However,it should be understood that the inlet 37 could also be located in, forexample, 39 a or 39 b and could be bubbled through the liquid 3 andtrapped within an interior portion of the localized atmosphere controlapparatus 35. Accordingly, precise locations of inlets and/or outlets inthe atmosphere control device 35 are a function of several factors.

FIG. 12 b shows a perspective view of first atmospheric controlapparatus 35 a in the foreground of the trough member 30 containedwithin the support housing 34. A second atmospheric control apparatus 35b is included and shows a control device 20 located thereon. “F” denotesthe longitudinal direction of flow of liquid 3 through the trough member30. A plurality of atmospheric control apparatuses 35 a, 35 b (as wellas 35 c, 35 d, etc. not shown in drawings) can be utilized instead of asingle atmosphere control device such as that shown in FIG. 11 c. Thereason for a plurality of localized atmosphere control devices 35 a-35_(x) is that different atmospheres can be present around each electrodeassembly, if desired. Accordingly, specific aspects of the adjustableplasma(s) 4 as well as specific constituents present in the liquid 3 andspecific aspects of the adjustable electrochemical reactions occurringat, for example, electrode(s) 5, will be a function of, among otherthings, the localized atmosphere. Accordingly, the use of one or morelocalized atmosphere control device 35 a provides tremendous flexibilityin the formation of desired constituents, nanoparticles, andnanoparticle solution mixtures.

FIG. 13 shows a perspective view of an alternative atmosphere controlapparatus 38 wherein the entire trough member 30 and support means 34are contained within the atmospheric control apparatus 38. In this case,for example, one or more gas inlets 37, 37′ can be provided along withone or more gas outlets 37 a, 37 a′. The exact positioning of the gasinlets 37, 37′ and gas outlets 37 a, 37 a′ on the atmospheric controlapparatus 38 is a matter of convenience, as well as a matter of thecomposition of the atmosphere. In this regard, if, for example, theatmosphere provided is heavier than air or lighter than air, inlet andoutlet locations can be adjusted accordingly. As discussed elsewhereherein, the gas inlet and gas outlet portions could be provided above orbelow the surface 2 of the liquid 3. Of course, when gas inlet portionsare provided below the surface 2 of the liquid 3 (not specifically shownin this Figure), it should be understood that bubbled (e.g., nanobubblesand/or microbubbles) of the gas inserted through the gas inlet 37 couldbe incorporated into the liquid 3, for at least a portion of theprocessing time. Such bubbles could be desirable reaction constituents(i.e., reactive with) the liquid 3 and/or constituents within the liquid3 and/or the electrode(s) 5, etc. Accordingly, the flexibility ofintroducing a localized atmosphere below the surface 2 of the liquid 3can provide additional processing control and/or processingenhancements.

FIG. 14 shows a schematic view of the general apparatus utilized inaccordance with the teachings of some of the preferred embodiments ofthe present invention. In particular, this FIG. 14 shows a sideschematic view of the trough member 30 containing a liquid 3 therein. Onthe top of the trough member 30 rests a plurality of control devices 20a-20 d (i.e., four of which are shown) which are, in this embodiment,removably attached thereto. The control devices 20 may of course bepermanently fixed in position when practicing various embodiments of theinvention. The precise number of control devices 20 (and correspondingelectrode(s) 1 and/or 5 as well as the configuration(s) of suchelectrodes) and the positioning or location of the control devices 20(and corresponding electrodes 1 and/or 5) are a function of variouspreferred embodiments of the invention some of which are discussed ingreater detail in the “Examples” section herein. However, in general, aninput liquid 3 (for example water) is provided to a liquid transportmeans 40 (e.g., a liquid peristaltic pump or a liquid pumping means forpumping liquid 3) for pumping the liquid water 3 into the trough member30 at a first-end 31 thereof. For example, the input liquid 3 (e.g.,water) could be introduced calmly or could be introduced in an agitatedmanner. Agitation includes, typically, the introduction of nanobubblesor microbubbles, which may or may not be desirable. If a gentleintroduction is desired, then such input liquid 3 (e.g., water) could begently provided (e.g., flow into a bottom portion of the trough).Alternatively, a reservoir (not shown) could be provided above thetrough member 30 and liquid 3 could be pumped into such reservoir. Thereservoir could then be drained from a lower portion thereof, a middleportion thereof or an upper portion thereof as fluid levels providedthereto reached an appropriate level. The precise means for deliveringan input liquid 3 into the trough member 30 at a first end 31 thereof isa function of a variety of design choices. Further, as mentioned aboveherein, it should be understood that additional input portions 31 couldexist longitudinally along different portions of the trough member 30.The distance “c-c” is also shown in FIG. 14. In general, the distance“c-c” (which corresponds to center-to-center longitudinal measurementbetween each control device 20) can be any amount or distance whichpermits desired functioning of the embodiments disclosed herein. Thedistance “c-c” should not be less than the distance “y” (e.g., ¼″-2″; 6mm-51 mm) and in a preferred embodiment about 1.5″ (about 38 mm) shownin, for example, FIGS. 1-4 and 7-9. The Examples show various distances“c-c”, however, to give a general understanding of the distance “c-c”,approximate distances vary from about 4″ to about 8″ (about 102 mm toabout 203 mm) apart, however, more or less separation is of coursepossible (or required) as a function of application of all of theprevious embodiments disclosed herein. In the Examples disclosed laterherein, preferred distances “c-c” in many of the Examples are about7″-8″ (about 177-203 mm).

In general, the liquid transport means 40 may include any means formoving liquids 3 including, but not limited to a gravity-fed orhydrostatic means, a pumping means, a peristaltic pumping means, aregulating or valve means, etc. However, the liquid transport means 40should be capable of reliably and/or controllably introducing knownamounts of the liquid 3 into the trough member 30. Once the liquid 3 isprovided into the trough member 30, means for continually moving theliquid 3 within the trough member 30 may or may not be required.However, a simple means includes the trough member 30 being situated ona slight angle θ (e.g., less than one degree to a few degrees) relativeto the support surface upon which the trough member 30 is located. Forexample, the difference in vertical height between an inlet portion 31and an outlet portion 32 relative to the support surface may be all thatis required, so long as the viscosity of the liquid 3 is not too high(e.g., any viscosity around the viscosity of water can be controlled bygravity flow once such fluids are contained or located within the troughmember 30). In this regard, FIG. 15 a shows cross-sectional views of thetrough member 30 forming an angle θ₁; and FIG. 15 b shows across-sectional view of the trough member 30 forming an angle θ₂, and avariety of acceptable angles for trough member 30 that handle variousviscosities, including low viscosity fluids such as water. The anglesthat are desirable for different cross-sections of the trough member 30and low viscosity fluids typically range between a minimum of about0.1-5 degrees for low viscosity fluids and a maximum of 5-10 degrees forhigher viscosity fluids. However, such angles are a function of avariety of factors already mentioned, as well as, for example, whether aspecific fluid interruption means or a dam 80 is included along a bottomportion or interface where the liquid 3 contacts the trough member 30.Such flow interruption means could include, for example, partialmechanical dams or barriers along the longitudinal flow direction of thetrough member 30. In this regard, θ₁ is approximately 5-10° and θ₂ isapproximately 0.1-5°. FIGS. 15 a and 15 b show a dam 80 near an outletportion 32 of the trough member 30. Multiple dam 80 devices can belocated at various portions along the longitudinal length of the troughmember 30. The dimension “j” can be, for example, about ⅛″-½″ (about3-13 mm) and the dimension “k” can be, for example, about ¼″-¾″ (about6-19 mm). The cross-sectional shape (i.e., “j-k” shape) of the dam 80can include sharp corners, rounded corners, triangular shapes,cylindrical shapes, and the like, all of which can influence liquid 3flowing through various portions of the trough member 30.

Further, when viscosities of the liquid 3 increase such that gravityalone is insufficient, other phenomena such as specific uses ofhydrostatic head pressure or hydrostatic pressure can also be utilizedto achieve desirable fluid flow. Further, additional means for movingthe liquid 3 along the trough member 30 could also be provided insidethe trough member 30, Such means for moving the liquid 3 includemechanical means such as paddles, fans, propellers, augers, etc.,acoustic means such as transducers, thermal means such as heaters (whichmay have additional processing benefits), etc. The additional means formoving the liquid 3 can cause liquid 3 to flow in differing amounts indifferent portions along the longitudinal length of the trough member30. In this regard, for example, if liquid 3 initially flowed slowlythrough a first longitudinal portion of the trough member 30, the liquid3 could be made to flow more quickly further downstream thereof by, forexample, as discussed earlier herein, changing the cross-sectional shapeof the trough member 30. Additionally, cross-sectional shapes of thetrough member 30 could also contain therein additional fluid handlingmeans which could speed up or slow down the rate the liquid 3 flowsthrough the trough member 30. Accordingly, great flexibility can beachieved by the addition of such means for moving the fluid 3.

FIG. 14 also shows a storage tank or storage vessel 41 at the end 32 ofthe trough member 30. Such storage vessel 41 can be any acceptablevessel and/or pumping means made of one or more materials which, forexample, do not negatively interact with the liquid 3 introduced intothe trough member 30 and/or products produced within the trough member30. Acceptable materials include, but are not limited to plastics suchas high density polyethylene (HDPE), glass, metal(s) (such a certaingrades of stainless steel), etc. Moreover, while a storage tank 41 isshown in this embodiment, the tank 41 should be understood as includinga means for distributing or directly bottling or packaging the liquid 3processed in the trough member 30.

FIGS. 16 a, 16 b and 16 c show perspective views of one preferredembodiment of the invention. In these FIGS. 16 a, 16 b and 16 c, eightseparate control devices 20 a-20 h are shown in more detail. Suchcontrol devices 20 can utilize one or more of the electrodeconfigurations shown in, for example, FIGS. 8 a, 8 b, 8 c and 8 d. Theprecise positioning and operation of the control devices 20 arediscussed in greater detail elsewhere herein. However, each of thecontrol devices 20 are separated by a distance “c-c” (see FIG. 14)which, in some of the preferred embodiments discussed herein, measuresabout 8″ (about 203 mm). FIG. 16 b includes use of two air distributingor air handling devices (e.g., fans 342 a and 342 b); and FIG. 16 cincludes use of two alternative or desirable air handling devices 342 cand 342 d. The fans 342 a, 342 b, 342 c and/or 342 d can be any suitablefan. For example a Dynatron DF124020BA, DC brushless, 9000 RPM, ballbearing fan measuring about 40 mm×40 mm×20 mm works well. Specifically,this fan has an air flow of approximately 10 cubic feet per minute.

FIG. 17 shows another perspective view of another embodiment of theapparatus according to another preferred embodiment wherein six controldevices 20 a-20 f (i.e., six electrode sets) are rotated approximately90 degrees relative to the eight control devices 20 a-20 h shown inFIGS. 16 a and 16 b. Accordingly, the embodiment corresponds generallyto the electrode assembly embodiments shown in, for example, FIGS. 9 a-9d.

FIG. 18 shows a perspective view of the apparatus shown in FIG. 16 a,but such apparatus is now shown as being substantially completelyenclosed by an atmosphere control apparatus 38. Such apparatus 38 is ameans for controlling the atmosphere around the trough member 30, or canbe used to isolate external and undesirable material from entering intothe trough member 30 and negatively interacting therewith. Further, theexit 32 of the trough member 30 is shown as communicating with a storagevessel 41 through an exit pipe 42. Moreover, an exit 43 on the storagetank 41 is also shown. Such exit pipe 43 can be directed toward anyother suitable means for storage, packing and/or handling the liquid 3.For example, the exit pipe 43 could communicate with any suitable meansfor bottling or packaging the liquid product 3 produced in the troughmember 30. Alternatively, the storage tank 41 could be removed and theexit pipe 42 could be connected directly to a suitable means forhandling, bottling or packaging the liquid product 3.

FIGS. 19 a, 19 b, 19 c and 19 d show additional cross-sectionalperspective views of additional electrode configuration embodimentswhich can be used according to the present invention.

In particular, FIG. 19 a shows two sets of electrodes 5 (i.e., 4 totalelectrodes 5 a, 5 b, 5 c and 5 d) located approximately parallel to eachother along a longitudinal direction of the trough member 30 andsubstantially perpendicular to the flow direction “F” of the liquid 3through the trough member 30. In contrast, FIG. 19 b shows two sets ofelectrodes 5 (i.e., 5 a, 5 b, 5 c and 5 d) located adjacent to eachother along the longitudinal direction of the trough member 30.

In contrast, FIG. 19 c shows one set of electrodes 5 (i.e., 5 a, 5 b)located substantially perpendicular to the direction of fluid flow “F”and another set of electrodes 5 (i.e., 5 c, 5 d) located substantiallyparallel to the direction of the fluid flow “F”. FIG. 19 d shows amirror image of the electrode configuration shown in FIG. 19 c. Whileeach of FIGS. 19 a, 19 b, 19 c and 19 d show only electrode(s) 5 it isclear that electrode(s) 1 could be substituted for some or all of thoseelectrode(s) 5 shown in each of FIGS. 19 a-19 d, and/or intermixedtherein (e.g., similar to the electrode configurations disclosed inFIGS. 8 a-8 d and 9 a-9 d). These alternative electrode configurationsprovide a variety of alternative electrode configuration possibilitiesall of which can result in different desirable nanoparticle ornanoparticle/solutions. It should now be clear to the reader thatelectrode assemblies located upstream of other electrode assemblies canprovide raw materials, pH changes, ingredients and/or conditioning orcrystal or structural changes to at least a portion of the liquid 3 suchthat reactions occurring at electrode(s) 1 and/or 5 downstream from afirst set of electrode(s) 1 and/or 5 can result in, for example, growthof nanoparticles, shrinking (e.g., partial or complete dissolution) ofnanoparticles, placing of different composition(s) on existingnanoparticles (e.g., surface feature comprising a variety of sizesand/or shapes and/or compositions which modify the performance of thenanoparticles), removing existing surface features or coatings onnanoparticles, etc. In other words, by providing multiple electrode setsof multiple configurations and one or more atmosphere control devicesalong with multiple adjustable electrochemical reactions and/oradjustable plasmas 4, the variety of constituents produced,nanoparticles, composite nanoparticles, thicknesses of shell layers(e.g., partial or complete) coatings or surface features on substratenanoparticles, are numerous, and the structure and/or composition of theliquid 3 can also be reliably controlled.

FIGS. 20 a-20 p show a variety of cross-sectional perspective views ofthe various electrode configuration embodiments possible and usable forall those configurations of electrodes 1 and 5 corresponding only to theembodiment shown in FIG. 19 a. In particular, for example, the number ofelectrodes 1 or 5 varies in these FIGS. 20 a-20 p, as well as thespecific locations of such electrode(s) 1 and 5 relative to each other.Of course, these electrode combinations 1 and 5 shown in FIGS. 20 a-20 pcould also be configured according to each of the alternative electrodeconfigurations shown in FIGS. 19 b, 19 c and 19 d (i.e., sixteenadditional figures corresponding to each of FIGS. 19 b, 19 c and 19 d)but additional figures have not been included herein for the sake ofbrevity. Specific advantages of these electrode assemblies, and others,are disclosed in greater detail elsewhere herein.

As disclosed herein, each of the electrode configurations shown in FIGS.20 a-20 p, depending on the particular run conditions, can result indifferent products coming from the mechanisms, apparatuses and processesof the inventive disclosures herein.

FIGS. 21 a, 21 b, 21 c and 21 d show cross sectional perspective viewsof additional embodiments of the present invention. The electrodearrangements shown in these FIGS. 21 a-21 d are similar in arrangementto those electrode arrangements shown in FIGS. 19 a, 19 b, 19 c and 19d, respectively. However, in these FIGS. 21 a-21 d a membrane or barrierassembly 50 is also included. In these embodiments of the invention, amembrane 50 is provided as a means for separating different productsmade at different electrode sets so that any products made by the set ofelectrodes 1 and/or 5 on one side of the membrane 50 can be at leastpartially isolated, or segregated, or substantially completely isolatedfrom certain products made from electrodes 1 and/or 5 on the other sideof the membrane 50. This membrane means 50 for separating or isolatingdifferent products may act as a mechanical barrier, physical barrier,mechano-physical barrier, chemical barrier, electrical barrier, etc.Accordingly, certain products made from a first set of electrodes 1and/or 5 can be at least partially, or substantially completely,isolated from certain products made from a second set of electrodes 1and/or 5. Likewise, additional serially located electrode sets can alsobe similarly situated. In other words, different membrane(s) 50 can beutilized at or near each set of electrodes 1 and/or 5 and certainproducts produced therefrom can be controlled and selectively deliveredto additional electrode sets 1 and/or 5 longitudinally downstreamtherefrom. Such membranes 50 can result in a variety of differentcompositions of the liquid 3 and/or nanoparticles or ions present in theliquid 3 produced in the trough member 30.

Possible ion exchange membranes 50 which function as a means forseparating for use with the present invention include Anionic membranesand Cationic membranes. These membranes can be homogenous, heterogeneousor microporous, symmetric or asymmetric in structure, solid or liquid,can carry a positive or negative charge or be neutral or bipolar.Membrane thickness may vary from as small as 100 micron to several mm.

Some specific ionic membranes for use with certain embodiments of thepresent invention include, but are not limited to:

-   -   Homogeneous polymerization type membranes such as sulfonated and        aminated styrene-divinylbenzene copolymers    -   condensation and heterogeneous membranes    -   perfluorocarbon cation exchange membranes    -   membrane chlor-alkali technology    -   Most of cation and anion exchange membranes used in the        industrial area are composed of derivatives of        styrene-divinylbenzene copolymer,        chloromethylstyrene-divinylbenzene copolymer or        vinylpyridines-divinylbenzene copolymer.    -   The films used that are the basis of the membrane are generally        polyethylene, polypropylene (ref. 'U, polytetrafluoroethylene,        PFA, FEP and so on.    -   Trifluoroacrylate and styrene are used in some cases.    -   Conventional polymers such as polyethersulfone, polyphenylene        oxide, polyvinyl chloride, polyvinylidene fluoride and so on.        Especially, sulfonation or chloromethylation and amination of        polyethersulfone or polyphenylene oxide.    -   Hydrocarbon ion exchange membranes are generally composed of        derivatives of styrene-divinylbenzene copolymer and other inert        polymers such as polyethylene, polyvinyl chloride and so on.

FIG. 22 a shows a perspective cross-sectional view of an electrodeassembly which corresponds to the electrode assembly 5 a, 5 b shown inFIG. 9 c. This electrode assembly can also utilize a membrane 50 forchemical, physical, chemo-physical and/or mechanical separation. In thisregard, FIG. 22 b shows a membrane 50 located between the electrodes 5a, 5 b. It should be understood that the electrodes 5 a, 5 b could beinterchanged with the electrodes 1 in any of the multiple configurationsshown, for example, in FIGS. 9 a-9 c. In the case of FIG. 22 b, themembrane assembly 50 has the capability of isolating partially orsubstantially completely, some or all of the products formed atelectrode 5 a, from some or all of those products formed at electrode 5b. Accordingly, various species formed at either of the electrodes 5 aand 5 b can be controlled so that they can sequentially react withadditional electrode assembly sets 5 a, 5 b and/or combinations ofelectrode sets 5 and electrode sets 1 in the longitudinal flow direction“F” that the liquid 3 undertakes along the longitudinal length of thetrough member 30. Accordingly, by appropriate selection of the membrane50, which products located at which electrode (or subsequent ordownstream electrode set) can be controlled. In a preferred embodimentwhere the polarity of the electrodes 5 a and 5 b are opposite, a varietyof different products may be formed at the electrode 5 a relative to theelectrode 5 b.

FIG. 22 c shows another different embodiment of the invention in across-sectional schematic view of a completely different alternativeelectrode configuration for electrodes 5 a and 5 b. In this case,electrode(s) 5 a (or of course electrode(s) 1 a) are located above amembrane 50 and electrode(s) 5 b are located below a membrane 50 (e.g.,are substantially completely submerged in the liquid 3). In this regard,the electrode, 5 b can comprise a plurality of electrodes or may be asingle electrode running along at least some or the entire longitudinallength of the trough member 30. In this embodiment, certain speciescreated at electrodes above the membrane 50 can be different fromcertain species created below the membrane 50 and such species can reactdifferently along the longitudinal length of the trough member 30. Inthis regard, the membrane 50 need not run the entire length of thetrough member 30, but may be present for only a portion of such lengthand thereafter sequential assemblies of electrodes 1 and/or 5 can reactwith the products produced therefrom. It should be clear to the readerthat a variety of additional embodiments beyond those expresslymentioned here would fall within the spirit of the embodiments expresslydisclosed.

FIG. 22 d shows another alternative embodiment of the invention wherebya configuration of electrodes 5 a (and of course electrodes 1) shown inFIG. 22 c are located above a portion of a membrane 50 which extends atleast a portion along the length of a trough member 30 and a secondelectrode (or plurality of electrodes) 5 b (similar to electrode(s) 5 bin FIG. 22 c) run for at least a portion of the longitudinal lengthalong the bottom of the trough member 30. In this embodiment ofutilizing multiple electrodes 5 a, additional operational flexibilitycan be achieved. For example, by splitting the voltage and current intoat least two electrodes 5 a, the reactions at the multiple electrodes 5a can be different from those reactions which occur at a singleelectrode 5 a of similar size, shape and/or composition. Of course thismultiple electrode configuration can be utilized in many of theembodiments disclosed herein, but have not been expressly discussed forthe sake of brevity. However, in general, multiple electrodes 1 and/or 5(i.e., instead of a single electrode 1 and/or 5) can add greatflexibility in products produced according to the present invention.Details of certain of these advantages are discussed elsewhere herein.

FIG. 23 a is a cross-sectional perspective view of another embodiment ofthe invention which shows a set of electrodes 5 corresponding generallyto that set of electrodes 5 shown in FIG. 19 a, however, the differencebetween the embodiment of FIG. 23 a is that a third set of electrode(s)5 e, 5 f have been provided in addition to those two sets of electrodes5 a, 5 b, 5 c and 5 d shown in FIG. 19 a. Of course, the sets ofelectrodes 5 a, 5 b, 5 c, 5 d, 5 d and 5 f can also be rotated 90degrees so they would correspond roughly to those two sets of electrodesshown in FIG. 19 b. Additional figures showing additional embodiments ofthose sets of electrode configurations have not been included here forthe sake of brevity.

FIG. 23 b shows another embodiment of the invention which alsopermutates into many additional embodiments, wherein membrane assemblies50 a and 50 b have been inserted between the three sets of electrodes 5a, 5 b; 5 c, 5 d; and 5 e, 5 f. It is of course apparent that thecombination of electrode configuration(s), number of electrode(s) andprecise membrane(s) means 50 used to achieve separation includes manyembodiments, each of which can produce different products when subjectedto the teachings of the present invention. More detailed discussion ofsuch products and operations of the present invention are discussedelsewhere herein.

FIGS. 24 a-24 e; 25 a-25 e; and 26 a-26 e show cross-sectional views ofa variety of membrane 50 locations that can be utilized according to thepresent invention. Each of these membrane 50 configurations can resultin different nanoparticles and/or nanoparticle/solution mixtures. Thedesirability of utilizing particular membranes in combination withvarious electrode assemblies add a variety of processing advantages tothe present invention. This additional flexibility results in a varietyof novel nanoparticle/nanoparticle solution mixtures.

Electrode Control Devices

The electrode control devices shown generally in, for example, FIGS. 2,3, 11, 12, 14, 16, 17 and 18 are shown in greater detail in FIG. 27 andFIGS. 28 a-281. In particular, FIG. 27 shows a perspective view of oneembodiment of an inventive control device 20. Further, FIGS. 28 a-28 lshow perspective views of a variety of embodiments of control devices20. FIG. 28 b shows the same control device 20 shown in FIG. 28 a,except that two electrode(s) 1 a/1 b are substituted for the twoelectrode(s) 5 a/5 b.

First, specific reference is made to FIGS. 27, 28 a and 28 b. In each ofthese three. Figures, a base portion 25 is provided, said base portionhaving a top portion 25′ and a bottom portion 25″. The base portion 25is made of a suitable rigid plastic material including, but not limitedto, materials made from structural plastics, resins, polyurethane,polypropylene, nylon, teflon, polyvinyl, etc. A dividing wall 27 isprovided between two electrode adjustment assemblies. The dividing wall27 can be made of similar or different material from that materialcomprising the base portion 25. Two servo-step motors 21 a and 21 b arefixed to the surface 25′ of the base portion 25. The step motors 21 a,21 b could be any step motor capable of slightly moving (e.g., on a 360degree basis, slightly less than or slightly more than 1 degree) suchthat a circumferential movement of the step motors 21 a/21 b results ina vertical raising or lowering of an electrode 1 or 5 communicatingtherewith. In this regard, a first wheel-shaped component 23 a is thedrivewheel connected to the output shaft 231 a of the drive motor 21 asuch that when the drive shaft 231 a rotates, circumferential movementof the wheel 23 a is created. Further, a slave wheel 24 a is caused topress against and toward the drivewheel 23 a such that frictionalcontact exists therebetween. The drivewheel 23 a and/or slavewheel 24 amay include a notch or groove on an outer portion thereof to assist inaccommodating the electrodes 1,5. The slavewheel 24 a is caused to bepressed toward the drivewheel 23 a by a spring 285 located between theportions 241 a and 261 a attached to the slave wheel 24 a. Inparticular, a coiled spring 285 can be located around the portion of theaxis 262 a that extends out from the block 261 a. Springs should be ofsufficient tension so as to result in a reasonable frictional forcebetween the drivewheel 24 a and the slavewheel 24 a such that when theshaft 231 a rotates a determined amount, the electrode assemblies 5 a, 5b, 1 a, 1 b, etc., will move in a vertical direction relative to thebase portion 25. Such rotational or circumferential movement of thedrivewheel 23 a results in a direct transfer of vertical directionalchanges in the electrodes 1,5 shown herein. At least a portion of thedrivewheel 23 a should be made from an electrically insulating material;whereas the slavewheel 24 a can be made from an electrically conductivematerial or an electrically insulating material, but preferably, anelectrically insulating material.

The drive motors 21 a/21 b can be any suitable drive motor which iscapable of small rotations (e.g., slightly below 1°/360° or slightlyabove 1°/360°) such that small rotational changes in the drive shaft 231a are translated into small vertical changes in the electrodeassemblies. A preferred drive motor includes a drive motor manufacturedby RMS Technologies model 1MC17-S04 step motor, which is a DC-poweredstep motor. This step motors 21 a/21 b include an RS-232 connection 22a/22 b, respectively, which permits the step motors to be driven by aremote control apparatus such as a computer or a controller.

With reference to FIGS. 27, 28 a and 28 b, the portions 271, 272 and 273are primarily height adjustments which adjust the height of the baseportion 25 relative to the trough member 30. The portions 271, 272 and273 can be made of same, similar or different materials from the baseportion 25. The portions 274 a/274 b and 275 a/275 b can also be made ofthe same, similar or different material from the base portion 25.However, these portions should be electrically insulating in that theyhouse various wire components associated with delivering voltage andcurrent to the electrode assemblies 1 a/1 b, 5 a/5 b, etc.

The electrode assembly specifically shown in FIG. 28 a compriseselectrodes 5 a and 5 b (corresponding to, for example, the electrodeassembly shown in FIG. 3 c). However, that electrode assembly couldcomprise electrode(s) 1 only, electrode(s) 1 and 5, electrode(s) 5 and1, or electrode(s) 5 only. In this regard, FIG. 28 b shows an assemblywhere two electrodes 1 a/1 b are provided instead of the twoelectrode(s) 5 a/5 b shown in FIG. 28 a. All other elements shown inFIG. 28 b are similar to those shown in FIG. 28 a.

With regard to the size of the control device 20 shown in FIGS. 27, 28 aand 28 b, the dimensions “L” and “W” can be any dimension whichaccommodates the size of the step motors 21 a/21 b, and the width of thetrough member 30. In this regard, the dimension “L” shown in FIG. 27needs to be sufficient such that the dimension “L” is at least as longas the trough member 30 is wide, and preferably slightly longer (e.g.,10-30%). The dimension “W” shown in FIG. 27 needs to be wide enough tohouse the step motors 21 a/21 b and not be so wide as to unnecessarilyunderutilize longitudinal space along the length of the trough member30. In one preferred embodiment of the invention, the dimension “L” isabout 7 inches (about 19 millimeters) and the dimension “W” is about 4inches (about 10.5 millimeters). The thickness “H” of the base member 25is any thickness sufficient which provides structural, electrical andmechanical rigidity for the base member 25 and should be of the order ofabout ¼″-¾″ (about 6 mm-19 mm). While these dimensions are not critical,the dimensions give an understanding of size generally of certaincomponents of one preferred embodiment of the invention.

Further, in each of the embodiments of the invention shown in FIGS. 27,28 a and 28 b, the base member 25 (and the components mounted thereto),can be covered by a suitable cover 290 (first shown in FIG. 28 d) toinsulate electrically, as well as creating a local protectiveenvironment for all of the components attached to the base member 25.Such cover 290 can be made of any suitable material which providesappropriate safety and operational flexibility. Exemplary materialsinclude plastics similar to that used for other portions of the troughmember 30 and/or the control device 20 and is preferably transparent.

FIG. 28 c shows a perspective view of an electrode guide assembly 280utilized to guide, for example, an electrode 5. Specifically, a topportion 281 is attached to the base member 25. A through-hole/slotcombination 282 a, 282 b and 282 c, all serve to guide an electrode 5therethrough. Specifically, the portion 283 specifically directs the tip9′ of the electrode 5 toward and into the liquid 3 flowing in the troughmember 30. The guide 280 shown in FIG. 28 c can be made of materialssimilar, or exactly the same, as those materials used to make otherportions of the trough member 30 and/or base member 25, etc.

FIG. 28 d shows a similar control device 20 as those shown in FIGS. 27and 28, but also now includes a cover member 290. This cover member 290can also be made of the same type of materials used to make the baseportion 25. The cover 290 is also shown as having 2 through-holes 291and 292 therein. Specifically, these through-holes can, for example, bealigned with excess portions of, for example, electrodes 5, which can beconnected to, for example, a spool of electrode wire (not shown in thesedrawings).

FIG. 28 e shows the cover portion 290 attached to the base portion 25with the electrodes 5 a, 5 b extending through the cover portion 290through the holes 292, 291, respectively.

FIG. 28 f shows a bottom-oriented perspective view of the control device20 having a cover 290 thereon. Specifically, the electrode guideapparatus 280 is shown as having the electrode 5 extending therethrough.More specifically, this FIG. 28 f shows an arrangement where anelectrode 1 would first contact a fluid 3 flowing in the direction “F”,as represented by the arrow in FIG. 28 f.

FIG. 28 g shows the same apparatus as that shown in FIG. 28 f with anatmosphere control device 35 added thereto. Specifically, the atmospherecontrol device is shown as providing a controlled atmosphere for theelectrode 1. Additionally, a gas inlet tube 286 is provided. This gasinlet tube provides for flow of a desirable gas into the atmospherecontrol device 35 such that plasmas 4 created by the electrode 1 arecreated in a controlled atmosphere.

FIG. 28 h shows the assembly of FIG. 28 g located within a trough member30 and a support means 341.

FIG. 28 i is similar to FIG. 28 f except now an electrode 5 is the firstelectrode that contacts a liquid 3 flowing in the direction of the arrow“F” within the trough member 30.

FIG. 28 j corresponds to FIG. 28 g except that the electrode 5 firstcontacts the flowing liquid 3 in the trough member 30.

FIG. 28 k shows a more detailed perspective view of the underside of theapparatus shown in the other FIG. 28's herein.

FIG. 28 l shows the control device 20 similar to that shown in FIGS. 28f and 28 i, except that two electrodes 1 are provided.

FIG. 29 shows another preferred embodiment of the invention wherein arefractory material 29 is combined with a heat sink 28 such that heatgenerated during processes practiced according to embodiments of theinvention generate sufficient amounts of heat that necessitate a thermalmanagement program. In this regard, the component 29 is made of, forexample, suitable refractory component, including, for example, aluminumoxide or the like. The refractory component 29 has a transversethrough-hole 291 therein which provides for electrical connections tothe electrode(s) 1 and/or 5. Further a longitudinal through-hole 292 ispresent along the length of the refractory component 29 such thatelectrode assemblies 1/5 can extend therethrough. The heat sink 28thermally communicates with the refractory member 29 such that any heatgenerated from the electrode assembly 1 and/or 5 is passed into therefractory member 29, into the heat sink 28 and out through the fins282, as well as the base portion 281 of the heat sink 28. The precisenumber, size, shape and location of the fins 282 and base portion 281are a function of, for example, the amount of heat required to bedissipated. Further, if significant amounts of heat are generated, acooling means such as a fan can be caused to blow across the fins 282.The heat sink is preferably made from a thermally conductive metal suchas copper, aluminum, etc.

FIG. 30 shows a perspective view of the heat sink of FIG. 29 as beingadded to the device shown in FIG. 27. In this regard, rather than theelectrode 5 a directly contacting the base portion 25, the refractorymember 29 is provided as a buffer between the electrodes 1/5 and thebase member 25.

A fan assembly, not shown in the drawings, can be attached to asurrounding housing which permits cooling air to blow across the coolingfins 282. The fan assembly could comprise a fan similar to a computercooling fan, or the like. A preferred fan assembly comprises, forexample, a Dynatron DF124020BA, DC brushless, 9000 RPM, ball bearing fanmeasuring about 40 mm×40 mm×20 mm works well. Specifically, this fan hasan air flow of approximately 10 cubic feet per minute.

FIG. 31 shows a perspective view of the bottom portion of the controldevice 20 shown in FIG. 30 a. In this FIG. 31, one electrode(s) 1 a isshown as extending through a first refractory portion 29 a and oneelectrode(s) 5 a is shown as extending through a second refractoryportion 29 b. Accordingly, each of the electrode assemblies expresslydisclosed herein, as well as those referred to herein, can be utilizedin combination with the preferred embodiments of the control deviceshown in FIGS. 27-31. In order for the control devices 20 to beactuated, two general processes need to occur. A first process involveselectrically activating the electrode(s) 1 and/or 5 (e.g., applyingpower thereto from a preferred power source 10), and the second generalprocess occurrence involves determining how much power is applied to theelectrode(s) and appropriately adjusting electrode 1/5 height inresponse to such determinations (e.g., manually and/or automaticallyadjusting the height of the electrodes 1/5). In the case of utilizing acontrol device 20, suitable instructions are communicated to the stepmotor 21 through the RS-232 ports 22 a and 22 b. Important embodimentsof components of the control device 20, as well as the electrodeactivation process, are discussed later herein.

Power Sources

A variety of power sources are suitable for use with the presentinvention. Power sources such as AC sources, DC sources, rectified ACsources of various polarities, etc., can be used. However, in thepreferred embodiments disclosed herein, an AC power source is utilizeddirectly, or an AC power source has been rectified to create a specificDC source of variable polarity.

FIG. 32 a shows a source of AC power 62 connected to a transformer 60.In addition, a capacitor 61 is provided so that, for example, lossfactors in the circuit can be adjusted. The output of the transformer 60is connected to the electrode(s) 1/5 through the control device 20. Apreferred transformer for use with the present invention is one thatuses alternating current flowing in a primary coil 601 to establish analternating magnetic flux in a core 602 that easily conducts the flux.

When a secondary coil 603 is positioned near the primary coil 601 andcore 602, this flux will link the secondary coil 603 with the primarycoil 601. This linking of the secondary coil 603 induces a voltageacross the secondary terminals. The magnitude of the voltage at thesecondary terminals is related directly to the ratio of the secondarycoil turns to the primary coil turns. More turns on the secondary coil603 than the primary coil 601 results in a step up in voltage, whilefewer turns results in a step down in voltage.

Preferred transformer(s) 60 for use in various embodiments disclosedherein have deliberately poor output voltage regulation made possible bythe use of magnetic shunts in the transformer 60. These transformers 60are known as neon sign transformers. This configuration limits currentflow into the electrode(s) 1/5. With a large change in output loadvoltage, the transformer 60 maintains output load current within arelatively narrow range.

The transformer 60 is rated for its secondary open circuit voltage andsecondary short circuit current. Open circuit voltage (OCV) appears atthe output terminals of the transformer 60 only when no electricalconnection is present. Likewise, short circuit current is only drawnfrom the output terminals if a short is placed across those terminals(in which case the output voltage equals zero). However, when a load isconnected across these same terminals, the output voltage of thetransformer 60 should fall somewhere between zero and the rated OCV. Infact, if the transformer 60 is loaded properly, that voltage will beabout half the rated OCV.

The transformer 60 is known as a Balanced Mid-Point Referenced Design(e.g., also formerly known as balanced midpoint grounded). This is mostcommonly found in mid to higher voltage rated transformers and most 60mA transformers. This is the only type transformer acceptable in a“mid-point return wired” system. The “balanced” transformer 60 has oneprimary coil 601 with two secondary coils 603, one on each side of theprimary coil 601 (as shown generally in the schematic view in FIG. 33a). This transformer 60 can in many ways perform like two transformers.Just as the unbalanced midpoint referenced core and coil, one end ofeach secondary coil 603 is attached to the core 602 and subsequently tothe transformer enclosure and the other end of the each secondary coil603 is attached to an output lead or terminal. Thus, with no connectorpresent, an unloaded 15,000 volt transformer of this type, will measureabout 7,500 volts from each secondary terminal to the transformerenclosure but will measure about 15,000 volts between the two outputterminals.

In alternating current (AC) circuits possessing a line power factor or 1(or 100%), the voltage and current each start at zero, rise to a crest,fall to zero, go to a negative crest and back up to zero. This completesone cycle of a typical sinewave. This happens 60 times per second in atypical US application. Thus, such a voltage or current has acharacteristic “frequency” of 60 cycles per second (or 60 Hertz) power.Power factor relates to the position of the voltage waveform relative tothe current waveform. When both waveforms pass through zero together andtheir crests are together, they are in phase and the power factor is 1,or 100%. FIG. 33 b shows two waveforms “V” (voltage) and “C” (current)that are in phase with each other and have a power factor of 1 or 100%;whereas FIG. 33 c shows two waveforms “V” (voltage) and “C” (current)that are out of phase with each other and have a power factor of about60%; both waveforms do not pass through zero at the same time, etc. Thewaveforms are out of phase and their power factor is less than 100%.

The normal power factor of most such transformers 60 is largely due tothe effect of the magnetic shunts 604 and the secondary coil 603, whicheffectively add an inductor into the output of the transformer's 60circuit to limit current to the electrodes 1/5. The power factor can beincreased to a higher power factor by the use of capacitor(s) 61 placedacross the primary coil 601 of the transformer, 60 which brings theinput voltage and current waves more into phase.

The unloaded voltage of any transformer 60 to be used in the presentinvention is important, as well as the internal structure thereof.Desirable unloaded transformers for use in the present invention includethose that are around 9,000 volts, 10,000 volts, 12,000 volts and 15,000volts. However, these particular unloaded volt transformer measurementsshould not be viewed as limiting the scope acceptable power sources asadditional embodiments. A specific desirable transformer for use withvarious embodiments of the invention disclosed herein is made byFranceformer, Catalog No. 9060-P-E which operates at: primarily 120volts, 60 Hz; and secondary 9,000 volts, 60 mA.

FIGS. 32 b and 32 c show another embodiment of the invention, whereinthe output of the transformer 60 that is input into the electrodeassemblies 1/5 has been rectified by a diode assembly 63 or 63′. Theresult, in general, is that an AC wave becomes substantially similar toa DC wave. In other words, an almost flat line DC output results(actually a slight 120 Hz pulse can sometimes be obtained). Thisparticular assembly results in two additional preferred embodiments ofthe invention (e.g., regarding electrode orientation). In this regard, asubstantially positive terminal or output and substantially negativeterminal or output is generated from the diode assembly 63. An oppositepolarity is achieved by the diode assembly 63′. Such positive andnegative outputs can be input into either of the electrode(s) 1 and/or5. Accordingly, an electrode 1 can be substantially negative orsubstantially positive; and/or an electrode 5 can be substantiallynegative and/or substantially positive. Further, when utilizing theassembly of FIG. 32 b, it has been found that the assemblies shown inFIGS. 29, 30 and 31 are desirable. In this regard, the wiring diagramshown in FIG. 32 b can generate more heat (thermal output) than thatshown in, for example, FIG. 32 a under a given set of operating (e.g.,power) conditions. Further, one or more rectified AC power source(s) canbe particularly useful in combination with the membrane assemblies shownin, for example, FIGS. 21-26.

FIG. 34 a shows 8 separate transformer assemblies 60 a-60 h each ofwhich is connected to a corresponding control device 20 a-20 h,respectively. This set of transformers 60 and control devices 20 isutilized in one preferred embodiment discussed in the Examples sectionlater herein.

FIG. 34 b shows 8 separate transformers 60 a′-60 h′, each of whichcorresponds to the rectified transformer diagram shown in FIG. 32 b.This transformer assembly also communicates with a set of controldevices 20 a-20 h and can be used as a preferred embodiment of theinvention.

FIG. 34 c shows 8 separate transformers 60 a″-60 h″, each of whichcorresponds to the rectified transformer diagram shown in FIG. 32 c.This transformer assembly also communicates with a set of controldevices 20 a-20 h and can be used as a preferred embodiment of theinvention.

Accordingly, each transformer assembly 60 a-60 h (and/or 60 a′-60 h′;and/or 60 a″-60 h″) can be the same transformer, or can be a combinationof different transformers (as well as different polarities). The choiceof transformer, power factor, capacitor(s) 61, polarity, electrodedesigns, electrode location, electrode composition, cross-sectionalshape(s) of the trough member 30, local or global electrode composition,atmosphere(s), local or global liquid 3 flow rate(s), liquid 3 localcomponents, volume of liquid 3 locally subjected to various fields inthe trough member 30, neighboring (e.g., both upstream and downstream)electrode sets, local field concentrations, the use and/or positionand/or composition of any membrane 50, etc., are all factors whichinfluence processing conditions as well as composition and/or volume ofconstituents produced in the liquid 3, nanoparticles andnanoparticle/solutions made according to the various embodimentsdisclosed herein. Accordingly, a plethora of embodiments can bepracticed according to the detailed disclosure presented herein.

Electrode Height Control/Automatic Control Device

A preferred embodiment of the invention utilizes the automatic controldevices 20 shown in various figures herein. The step motors 21 a and 21b shown in, for example, FIGS. 27-31, are controlled by an electricalcircuit diagrammed in each of FIGS. 35, 36 a, 36 b and 36 c. Inparticular, the electrical circuit of FIG. 35 is a voltage monitoringcircuit. Specifically, voltage output from each of the output legs ofthe secondary coil 603 in the transformer 60 are monitored over thepoints “P-Q” and the points “P′-Q”. Specifically, the resistor denotedby “R_(L)” corresponds to the internal resistance of the multi-metermeasuring device (not shown). The output voltages measured between thepoints “P-Q” and “P′-Q′” typically, for several preferred embodimentsshown in the Examples later herein, range between about 200 volts andabout 4,500 volts. However, higher and lower voltages can work with manyof the embodiments disclosed herein. In the Examples later herein,desirable target voltages have been determined for each electrode set 1and/or 5 at each position along a trough member 30. Such desirabletarget voltages are achieved as actual applied voltages by, utilizing,for example, the circuit control shown in FIGS. 36 a, 36 b and 36 c.These FIG. 36 refer to sets of relays controlled by a Velleman K8056circuit assembly (having a micro-chip PIC16F630-I/P). In particular, avoltage is detected across either the “P-Q” or the “P′-Q′” locations andsuch voltage is compared to a predetermined reference voltage (actuallycompared to a target voltage range). If a measured voltage across, forexample, the points “P-Q” is approaching a high-end of a predeterminedvoltage target range, then, for example, the Velleman K8056 circuitassembly causes a servo-motor 21 (with specific reference to FIG. 28 a)to rotate in a clockwise direction so as to lower the electrode 5 atoward and/or into the fluid 3. In contrast, should a measured voltageacross either of the points “P-Q” or “P′-Q′” be approaching a lower endof a target voltage, then, for example, again with reference to FIG. 28a, the server motor 21 a will cause the drive-wheel 23 a to rotate in acounter-clockwise position thereby raising the electrode 5 a relative tothe fluid 3.

Each set of electrodes in each embodiment of the invention has anestablished target voltage range. The size or magnitude of acceptablerange varies by an amount between about 1% and about 10%-15% of thetarget voltage. Some embodiments of the invention are more sensitive tovoltage changes and these embodiments should have, typically, smalleracceptable voltage ranges; whereas other embodiments of the inventionare less sensitive to voltage and should have, typically, largeracceptable ranges. Accordingly, by utilizing the circuit diagram shownin FIG. 35, actual voltages output from the secondary coil 603 of thetransformer 60 are measured at “R_(L)” (across the terminals “P-Q” and“P′-Q′”), and are then compared to the predetermined voltage ranges. Theservo-motor 21 responds by rotating a predetermined amount in either aclockwise direction or a counter-clockwise direction, as needed.Moreover, with specific reference to FIG. 36, it should be noted that aninterrogation procedure occurs sequentially by determining the voltageof each electrode, adjusting height (if needed) and then proceeding tothe next electrode. In other words, each transformer 60 is connectedelectrically in a manner shown in FIG. 35. Each transformer 60 andassociated measuring points “P-Q” and “P′-Q′” are connected to anindividual relay. For example, the points “P-Q” correspond to relaynumber 501 in FIG. 36 a and the points “P′-Q′” correspond to the relay502 in FIG. 36 a. Accordingly, two relays are required for eachtransformer 60. Each relay, 501, 502, etc., sequentially interrogates afirst output voltage from a first leg of a secondary coil 603 and then asecond output voltage from a second leg of the secondary coil 603; andsuch interrogation continues onto a first output voltage from a secondtransformer 60 b on a first leg of its secondary coil 603, and then onto a second leg of the secondary coil 603, and so on.

The computer or logic control for the discussed interrogation voltageadjustment techniques are achieved by any conventional program orcontroller, including, for example, in a preferred embodiment, standardvisual basic programming steps utilized in a PC. Such programming stepsinclude interrogating, reading, comparing, and sending an appropriateactuation symbol to increase or decrease voltage (e.g., raise or loweran electrode relative to the surface 2 of the liquid 3). Such techniquesshould be understood by an artisan of ordinary skill.

Examples 1-12

The following examples serve to illustrate certain embodiments of theinvention but should not to be construed as limiting the scope of thedisclosure.

In general, each of the 12 Examples utilize certain embodiments of theinvention associated with the apparatuses generally shown in FIGS. 16 band 16 c. Specific differences in processing and apparatus will beapparent in each Example. The trough member 30 was made from plexiglass,all of which had a thickness of about 3 mm-4 mm (about ⅛″). The supportstructure 34 was also made from plexiglass which was about ¼″ thick(about 6-7 mm thick). The cross-sectional shape of the trough member 30corresponded to that shape shown in FIG. 10 b (i.e., a truncated “V”).The base portion “R” of the truncated “V” measured about 0.5″ (about 1cm), and each side portion “S”, “S′” measured about 1.5″ (about 3.75cm). The distance “M” separating the side portions “S”, “S′” of theV-shaped trough member 30 was about 2¼″-2 5/16″ (about 5.9 cm) (measuredfrom inside to inside). The thickness of each portion also measuredabout ⅛″ (about 3 mm) thick. The longitudinal length “L_(T)” (refer toFIG. 11 a) of the V-shaped trough member 30 measured about 6 feet (about2 meters) long from point 31 to point 32. The difference in verticalheight from the end 31 of the trough member 30 to the end 32 was about¼-½″ (about 6-12.7 mm) over its 6 feet length (about 2 meters) (i.e.,less than 1°).

Purified water (discussed later herein) was used as the liquid 3 in allof Examples 1-12. The depth “d” (refer to FIG. 10 b) of the water 3 inthe V-shaped trough member 30 was about 7/16″ to about ½″ (about 11 mmto about 13 mm) at various points along the trough member 30. The depth“d” was partially controlled through use of the dam 80 (shown in FIGS.15 a and 15 b). Specifically, the dam 80 was provided near the end 32and assisted in creating the depth “d” (shown in FIG. 10 b) to be about7/6″-½″ (about 11-13 mm) in depth. The height “j” of the dam 80 measuredabout ¼″ (about 6 mm) and the longitudinal length “k” measured about ½″(about 13 mm). The width (not shown) was completely across the bottomdimension “R” of the trough member 30. Accordingly, the total volume ofwater 3 in the V-shaped trough member 30 during operation thereof wasabout 26 in³ (about 430 ml).

The rate of flow of the water 3 in the trough member 30 was about150-200 ml/minute, depending on which Example was being practiced.Specifically, for example, silver-based and copper-basednanoparticle/solution raw materials made in Examples 1-3 and 5 allutilized a flow rate of about 200 ml/minute; and a zinc-basednanoparticle/solution raw material made in Example 4 utilized a flowrate of about 150 ml/minute. Such flow of water 3 was obtained byutilizing a Masterflex® L/S pump drive 40 rated at 0.1 horsepower,10-600 rpm. The model number of the Masterflex® pump 40 was 77300-40.The pump drive had a pump head also made by Masterflex® known asEasy-Load Model No. 7518-10. In general terms, the head for the pump 40is known as a peristaltic head. The pump 40 and head were controlled bya Masterflex® LS Digital Modular Drive. The model number for the DigitalModular Drive is 77300-80. The precise settings on the Digital ModularDrive were, for example, 150 milliliters per minute for Example 4 and200 mL/minute for the other Examples 1-3 and 5. Tygon® Tubing having adiameter of ¼″ (i.e., size 06419-25) was placed into the peristaltichead. The tubing was made by Saint Gobain for Masterflex®. One end ofthe tubing was delivered to a first end 31 of the trough member 30 by aflow diffusion means located therein. The flow diffusion means tended tominimize disturbance and bubbles in water 3 introduced into the troughmember 30 as well as any pulsing condition generated by the peristalticpump 40. In this regard, a small reservoir served as the diffusion meansand was provided at a point vertically above the end 31 of the troughmember 30 such that when the reservoir overflowed, a relatively steadyflow of water 3 into the end 31 of the V-shaped trough member 30occurred.

Additionally, the plastic portions of the control devices 20 were alsomade from plexiglass having a thickness of about ⅛″ (about 3 mm). Withreference to FIG. 27, the control devices 20 had a dimension “w”measuring about 4″ (about 10 cm) and a dimension “L” measuring about7.5″ (about 19 cm). The thickness of the base portion 25 was about 1/4″(about 0.5 cm). All of the other components shown in FIG. 27 are drawnvery close to scale. All individual components attached to surfaces 25′and 25″ were also made of plexiglass which were cut to size and gluedinto position.

With regard to FIGS. 16 b and 16 c, 8 separate electrode sets (Set 1,Set 2, Set 3,-Set 8) were attached to 8 separate control devices 20.Each of Tables 3-7 refers to each of the 8 electrode sets by “Set #”.Further, within any Set #, electrodes 1 and 5, similar to the electrodeassemblies shown in FIGS. 3 a and 3 c were utilized. Each electrode ofthe 8 electrode sets was set to operate within specific target voltagerange. Actual target voltages are listed in each of Tables 3-7. Thedistance “c-c” (with reference to FIG. 14) from the centerline of eachelectrode set to the adjacent electrode set is also represented.Further, the distance “x” associated with any electrode(s) 1 utilized isalso reported. For any electrode 5's, no distance “x” is reported. Otherrelevant distances are reported, for example, in each of Tables 3-7.

The size and shape of each electrode 1 utilized was about the same. Theshape of each electrode 1 was that of a right triangle with measurementsof about 14 mm×23 mm×27 mm. The thickness of each electrode 1 was about1 mm. Each triangular-shaped electrode 1 also had a hole therethrough ata base portion thereof, which permitted the point formed by the 23 mmand 27 mm sides to point toward the surface 2 of the water 3. Thematerial comprising each electrode 1 was 99.95% pure (i.e., 3N5) unlessotherwise stated herein. When silver was used for each electrode 1, theweight of each electrode was about 2 grams. When zinc was used for eachelectrode 1, the weight of each electrode was about 1.1 grams. Whencopper was used for each electrode 1, the weight of each electrode wasabout 1.5 grams.

The wires used to attach the triangular-shaped electrode 1 to thetransformer 60 were, for Examples 1-4, 99.95% (3N5) silver wire, havinga diameter of about 1.016 mm. The wire used to attach the triangularshaped electrode 1 in Example 5 was 99.95% pure (3N5) copper wire; alsohaving a diameter of about 1.016 mm. Accordingly, a small loop of wirewas placed through the hole in each electrode 1 to electrically connectthereto.

The wires used for each electrode 5 comprised 99.95% pure (3N5) eachhaving a diameter of about 1.016 mm. The composition of the electrodes 5in Examples 1-3 was silver; in Example 4 was zinc and in Example 5 wascopper. All materials for the electrodes 1/5 were obtained from ESPIhaving an address of 1050 Benson Way, Ashland, Oreg. 97520.

The water 3 used in Examples 1-12 as an input into the trough member 30was produced by a Reverse Osmosis process and deionization process. Inessence, Reverse Osmosis (RO) is a pressure driven membrane separationprocess that separates species that are dissolved and/or suspendedsubstances from the ground water. It is called “reverse” osmosis becausepressure is applied to reverse the natural flow of osmosis (which seeksto balance the concentration of materials on both sides of themembrane). The applied pressure forces the water through the membraneleaving the contaminants on one side of the membrane and the purifiedwater on the other. The reverse osmosis membrane utilized several thinlayers or sheets of film that are bonded together and rolled in a spiralconfiguration around a plastic tube. (This is also known as a thin filmcomposite or TFC membrane.) In addition to the removal of dissolvedspecies, the RO membrane also separates out suspended materialsincluding microorganisms that may be present in the water. After ROprocessing a mixed bed deionization filter was used. The total dissolvedsolvents (“TDS”) after both treatments was about 0.2 ppm, as measured byan Accumet® AR20 pH/conductivity meter.

Example 1 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT059 and AT038

This Example utilizes 99.95% pure silver electrodes 1 and 5. Table 3summarizes portions of electrode design, location and operatingvoltages. As can be seen from Table 3, the target voltages were set to alow of about 550 volts and to a high of about 2,100 volts.

Further, bar charts of the actual and target voltages for each electrodein each of the 8 electrode sets, Set #1-Set#8, are shown in FIG. 37 a.Still further, the actual recorded voltages as well as a function of thetime of day is shown in each of FIGS. 37 b-37 i. Accordingly, the datacontained in Table 3, as well as FIGS. 37 a-37 i, give a completeunderstanding of the electrode design in each electrode set as well asthe target and actual voltages applied to each electrode for theduration of the manufacturing process.

TABLE 3 AT059 Flow Rate: 200 ml/min Room Temperature 23 C. RelativeHumidity 23% Target Electrode Voltage Distance Distance Average Set #Set # (kV) “c-c” in/mm “x” in/mm Voltage (kV) 7/177.8* 1 1a 2.110.29/7.37 2.05 5a 1.83 N/A 1.83 8/203.2 2 1b 1.09 0.22/5.59 1.16 5b 1.14N/A 1.14 8/203.2 3 1c 1.02 0.22/5.59 0.96 5c 0.92 N/A 0.92 8/203.2 4 1d0.90 0.15/3.81 0.88 5d 0.78 N/A 0.77 9/228.6 5 1e 1.26 0.22/5.59 1.34 5e0.55 N/A 0.55 8/203.2 6 1f 0.96 0.22/5.59 0.99 5f 0.72 N/A 0.72 8/203.27 1g 0.89 0.22/5.59 0.81 5g 0.70 N/A 0.70 8/203.2 8 1h 0.63 0.15/3.810.59 5h 0.86 N/A 0.85 8/203.2** Output Water Temperature 67 C. *Distancefrom water inlet to center of first electrode set **Distance from centerof last electrode set to water outlet

Example 2 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT060 and AT036

Table 4 contains information similar to that data shown in Table 3relating to electrode set design, voltages, distances, etc. It is clearfrom Table 4 that the electrode configurations Set #1 and Set #2 werethe same as of Set #'s 1-8 in Table 3 and Example 1. Further electrodeSets 3-8 are all configured in the same manner and corresponded to adifferent electrode configuration from Set #1 and Set #2 herein, whichelectrode configuration corresponds to that configuration shown in FIG.8 c.

TABLE 4 AT060 Flow Rate: 200 ml/min Room Temperature 23 C. RelativeHumidity 23% Average Electrode Target Voltage Distance Distance VoltageSet # Set # (kV) “c-c” in/mm “x” in/mm (kV) 7/177.8* 1 1a 2.41 0.37/9.42.14 5a 1.87 N/A 1.86 8/203.2 2 1b 1.33 0.26/6.6 1.33 5b 1.13 N/A 1.138/203.2 3 5c 0.79 N/A 0.80 5c′ 0.78 N/A 0.79 8/203.2 4 5d 0.85 N/A 0.865d′ 0.88 N/A 0.91 9/228.6 5 5e 1.07 N/A 1.06 5e′ 0.70 N/A 0.69 8/203.2 65f 0.94 N/A 0.92 5f′ 0.92 N/A 0.90 8/203.2 7 5g 1.02 N/A 1.00 5g′ 0.93N/A 0.91 8/203.2 8 5h 0.62 N/A 0.63 5h′ 0.80 N/A 0.83 8/203.2** OutputWater Temperature 73 C. *Distance from water inlet to center of firstelectrode set **Distance from center of last electrode set to wateroutlet

FIG. 38 a shows a bar chart of target and actual average voltages foreach electrode in each of the 8 electrode sets (i.e., Set #1-Set #8).

FIGS. 38 b-38 i show actual voltages applied to the electrodes for eachof the 8 electrode sets.

The product produced according to Example 2 is referred to herein as“AT060”.

Example 3 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT031

Table 5 herein sets forth electrode design and target voltages for eachof the 16 electrodes in each of the eight electrode sets (i.e., Set#1-Set #8) utilized to form the product formed in this example referredto herein as “AT031”.

TABLE 5 AT031 Flow Rate: 200 ml/min Room Temperature 22.5 C. RelativeHumidity 47% Target Electrode Voltage Distance Distance Average Set #Set # (kV) “c-c” in/mm “x” in/mm Voltage (kV) 7/177.8* 1 1a 2.240.22/5.59 2.28 5a 1.84 N/A 1.84 8/203.2 2 5b 1.35 N/A 1.36 5b′ 1.55 N/A1.55 8/203.2 3 5c 1.46 N/A 1.46 5c′ 1.54 N/A 1.54 8/203.2 4 1d 1.620.19/4.83 1.61 5d 1.25 N/A 1.27 9/228.6 5 5e 1.21 N/A 1.21 5e′ 0.82 N/A0.82 8/203.2 6 5f 0.99 N/A 1.06 5f′ 0.92 N/A 0.92 8/203.2 7 5g 1.02 N/A1.03 5g′ 0.96 N/A 0.95 8/203.2 8 5h 1.00 N/A 1.00 5h′ 0.97 N/A 1.238/203.2** Output Water Temperature 83 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

FIG. 39 a shows a bar chart of target and actual average voltagesapplied for each of the 16 electrodes in each of the 8 electrode sets.

FIGS. 39 b-39 i show the actual voltages applied to each of the 16electrodes in each of the 8 electrode sets as a function of time.

It should be noted that electrode Set #1 was the same in this Example 3as in each of Examples 1 and 2 (i.e., an electrode configuration of1/5). Another 1/5 configuration was utilized for each of the otherelectrode sets, namely Set #2 and Set #'s 5-8 were all configured in amanner according to a 5/5 configuration.

Example 4 Manufacturing Zinc-Based Nanoparticles/Nanoparticle SolutionsBT006 and BT004

Material designated herein as “BT006” was manufactured in accordancewith the disclosure of Example 4. Similar to Examples 1-3, Table 6herein discloses the precise electrode combinations in each of the 8electrode sets (i.e, Set #1-Set #8). Likewise, target and actualvoltage, distances, etc., are also reported. It should be noted that theelectrode set assembly of Example 4 is similar to the electrode setassembly used in Example 1, except that 99.95% pure zinc was used onlyfor the electrodes 5. The triangular-shaped portion of the electrodes 1also comprised the same purity zinc, however the electrical connectionsto the triangular-shaped electrodes were all 99.95% pure silver-wire,discussed above herein. Also, the flow rate of the reaction 3 was lowerin this Example then in all the other Examples.

TABLE 6 BT006 Flow Rate: 150 ml/min Room Temp 73.2-74.5 F. Relativehumidity 21-22% Average Electrode Target Voltage Distance DistanceVoltage Set # Set # (kV) “c-c” in/mm “x” in/mm (kV) 7/177.8* 1 1a 1.910.29/7.37 1.88 5a 1.64 N/A 1.64 8/203.2 2 1b 1.02 0.22/5.59 1.05 5b 1.09N/A 1.08 8/203.2 3 1c 0.91 0.22/5.59 0.90 5c 0.81 N/A 0.82 8/203.2 4 1d0.84 0.15/3.81 0.86 5d 0.74 N/A 0.75 9/228.6 5 1e 1.40 0.22/5.59 1.40 5e0.54 N/A 0.55 8/203.2 6 1f 0.93 0.22/5.59 0.91 5f 0.61 N/A 0.63 8/203.27 1g 0.72 0.22/5.59 0.82 5g 0.75 N/A 0.75 8/203.2 8 1h 0.64 0.15/3.810.60 5h 0.81 N/A 0.81 8/203.2** Output Water Temperature 64 C. *Distancefrom water inlet to center of first electrode set **Distance from centerof last electrode set to water outlet

FIG. 40 a shows a bar chart of the target and actual applied averagevoltages utilized for each of the 16 electrodes in the 8 electrode sets.Also, FIGS. 40 b-40 i show the actual voltages applied to each of the 16electrodes as a function of time.

Example 5 Manufacturing Copper-Based Nanoparticles/NanoparticleSolutions CT006

A copper-based nanoparticle solution designated as “CT006” was madeaccording to the procedures disclosed in Example 5. In this regard,Table 7 sets forth pertinent operating parameters associated with eachof the 16 electrodes in the 8 electrode sets.

TABLE 7 CT006 Flow Rate: 200 ml/min Relative Humidity 48% RoomTemperature 23.1 C. Average Electrode Target Voltage Distance DistanceVoltage Set # Set # (kV) “c-c” (in) “x” (in) (kV) 7/177.8* 1 1a 2.170.44/11.18 2.21 5a 1.75 N/A 1.74 8/203.2 2 5b 1.25 N/A 1.24 5b′ 1.64 N/A1.63 8/203.2 3 1c 1.45 0.22/5.59  1.43 5c 0.83 N/A 0.83 8/203.2 4 5d0.77 N/A 0.77 5d′ 0.86 N/A 0.86 9/228.6 5 5e 1.17 N/A 1.15 5e′ 0.76 N/A0.76 8/203.2 6 5f 0.85 N/A 0.84 5f′ 0.84 N/A 0.83 8/203.2 7 5g 0.99 N/A0.99 5g′ 0.87 N/A 0.86 8/203.2 8 5h 0.85 N/A 0.85 5h′ 1.10 N/A 1.098/203.2** Output Water Temperature 79 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

Further, FIG. 41 a shows a bar chart of each of the average actualvoltages applied to each of the 16 electrodes in the 8 electrode sets.It should be noted that the electrode configuration was slightlydifferent than the electrode configuration in each of Examples 1-4.Specifically, electrode Set #'s 1 and 3 were of the 1/5 configuration,and all other the Sets were of the 5/5 configuration.

FIG. 41 b-41 i show the actual voltages applied to each of the 16electrodes as a function of time. As above, the wires utilized for eachof the electrode(s) 1 and 5 comprised wires of a diameter of about 0.04″(1.016 mm) and a 99.95% purity.

Characterization of Materials of Examples 1-5 and Mixtures Thereof

Each of the silver-based nanoparticles and nanoparticle/solutions madein Examples 1-3 (AT-059/AT-038), (AT060/AT036) and (AT031),respectively; as well as the zinc nanoparticles andnanoparticle/solutions made in Example 4 (BT-004); and the coppernanoparticles and nanoparticle-based/solutions made in Example 5(CT-006) were physically characterized by a variety of techniques.Specifically, Tables 8 and 9 herein show each of the 5 “raw materials”made according to Examples 1-5 as well as 10 solutions or mixtures madetherefrom, each of the solutions being designated “GR1-GR10” orGR1B-GR10B″. The amount by volume of each of the “raw materials” isreported for each of the 10 solutions manufactured. Further, atomicabsorption spectroscopy (“AAS”) was performed on each of the rawmaterials of Examples 1-5 as well as on each of the 10 solutionsGR1-GR10 derived therefrom. The amount of silver constituents, zincconstituents and/or copper constituents therein were thus determined.The atomic absorption spectroscopy results (AAS) are reported bymetallic-based constituent.

TABLE 8 Solution Contents Analytical Results Silver % Zinc % by Copper %by Ag ppm Zn ppm Cu ppm Metal ppm NO2 NO3 ID Constituent by VolumeConstituent Volume Constituent Volume (AAS) (AAS) (AAS) (Ionic) (ppm)(ppm) pH AT- AT-036 100.0% 43.8 30.8  38.9 2.3 5.31 036 AT- AT-031100.0% 41.3 23.3  41.3 15 5.23 031 AT- AT-038 100.0% 46 24.3  N/A 11.73.34 038 BT- BT-004 100.0% 23.1 ** N/A 33.7 3.52 004 CT- CT-006 100.0%9.2 17.3 5.20 4.38 006 GR1 AT-036 22.8% BT-004 43.3% CT-006 33.9% 9.410.5 3.3 *  6.2 19.7 3.93 GR2 AT-031 24.2% BT-004 43.3% CT-006 32.5% 8.711.4 2.9 *  7.2 21.5 3.86 GR3 AT-038 21.7% BT-004 43.3% CT-006 35.0% 9.110.8 3.1 * N/A 23.7 3.64 GR4 AT-036 22.8% BT-004 77.2% 9.5 19.7 5.6 N/A36.7 3.66 GR5 AT-031 24.2% BT-004 75.8% 10.4 18.8 5.9 N/A 26.6 3.68 GR6AT-038 21.7% BT-004 78.3% 7.6 N/A 25.3 3.5 GR7 AT-036 45.7% BT-004 54.3%17.3 13.3 8.9 N/A 19.6 3.83 GR8 AT-036 16.0% BT-004 84.0% 7.4 20.0 5.1N/A 29.2 3.61 GR9 AT-036 70.0% BT-004 10.0% CT-006 20.0% 27.1 2.4 1.8 *36.2 3.1 4.54 GR10 AT-36/31/39 34.3% BT-004 65.7% 13.2 15.6 7.3 N/A 23.43.62 N/A ph is out of testing range * Can not be tested due to silverand copper interaction ** Zinc can not be tested with device

The AAS values were obtained from a Perkin Elmer AAnalyst 300Spectrometer system. The samples from Examples 1-5 and SolutionsGR1-GR10 were prepared by adding a small amount of nitric acid orhydrochloric acid (usually 2% of final volume) and then dilution to adesirable characteristic concentration range or linear range of thespecific element to improve accuracy of the result. The “desirable”range is an order of magnitude estimate based on production parametersestablished during product development. For pure metals analysis, aknown amount of feedstock material is digested in a known amount of acidand diluted to ensure that the signal strength of the absorbance will bewithin the tolerance limits and more specifically the most accuraterange of the detector settings, better known as the linear range.

The specific operating procedure for the Perkin Elmer AAnalyst 300system is as follows:

I) Principle

-   -   The Perkin Elmer AAnalyst 300 system consists of a high        efficiency burner system with a Universal GemTip nebulizer and        an atomic absorption spectrometer. The burner system provides        the thermal energy necessary to dissociate the chemical        compounds, providing free analyte atoms so that atomic        absorption occurs. The spectrometer measures the amount of light        absorbed at a specific wavelength using a hollow cathode lamp as        the primary light source, a monochromator and a detector. A        deuterium arc lamp corrects for background absorbance caused by        non-atomic species in the atom cloud.        II) Instrument Setup    -   A) Empty waste container to mark. Add deionized water to drain        tubing to ensure that water is present in the drain system float        assembly.    -   B) Ensure that the appropriate Hollow Cathode Lamp for the        analyte to be analyzed is properly installed in the turret.    -   C) Power AAnalyst 300 and computer ON.    -   E) After the AAnalyst 300 has warmed up for approximately 3        minutes, start the AAWin Analyst software    -   F) Recall Method to be analyzed.    -   G) Ensure that the correct Default Conditions are entered.    -   H) Align the Hollow Cathode Lamp.        -   1) Check that a proper peak and energy level has been            established for the specific lamp.        -   2) Adjust the power and frequency of the lamp settings to            obtain maximum energy.    -   I) Store Method changes in Parameter Entry, Option, Store and #.    -   J) Adjust Burner height.        -   1) Place a white sheet of paper behind the burner to confirm            the location of the light beam.        -   2) Lower the burner head below the light beam with the            vertical adjustment knob.        -   3) Press Cont (Continuous) to display an absorbance value.        -   4) Press A/Z to Autozero.        -   5) Raise the burner head with the vertical adjustment knob            until the display indicates a slight absorbance (0.002).            Slowly lower the head until the display returns to zero.            Lower the head an additional quarter turn to complete the            adjustment.    -   K) Ignite flame.        -   1) Turn Fume Hood switch ON.        -   2) Open air compressor valve. Set pressure to 50 to 65 psi.        -   3) Open acetylene gas cylinder valve. Set output pressure to            12 to 14 psi. Replace cylinder when pressure falls to 85 psi            to prevent valve and tubing damage from the presence of            acetone.        -   4) Press Gases On/Off. Adjust oxidant flow to 4 Units.        -   5) Press Gases On/Off. Adjust acetylene gas flow to 2 Units.        -   6) Press Flame On/Off to turn flame on.            -   Note: Do not directly view the lamp or flame without                protective ultraviolet radiation eyewear.    -   L) Aspirate deionized water through the burner head several        minutes.    -   M) Adjust Burner Position and Nebulizer.        -   1) Aspirate a standard with a signal of approximately 0.2            absorbance units.        -   2) Obtain maximum burner position absorbance by rotating the            horizontal and rotational adjustment knobs.        -   3) Loosen the nebulizer locking ring by turning it            clockwise. Slowly turn the nebulizer adjustment knob to            obtain maximum absorbance. Lock the knob in place with the            locking ring.        -   Note: An element, such as Magnesium, which is at a            wavelength where gases do not absorb is optimal for            adjusting the Burner and Nebulizer.    -   N) Allow 30 minutes to warm-up flame and lamp.        III) Calibration Procedure    -   A) Calibrate with standards that bracket the sample        concentrations.    -   B) WinAA Analyst software will automatically create a        calibration curve for your sample readings. But check to ensure        that proper absorption is established with each calibration        standard.    -   C) Enter Standard Concentration Values in the Default Conditions        to calculate an AAnalyst 300 standard curve.        -   1) Enter the concentration of the lowest standard for STD1            using significant digits.        -   2) Enter the concentrations of the other standards of the            calibration curve in ascending order and the concentration            of the reslope standard.        -   3) Autozero with the blank before each standard.        -   4) Aspirate Standard 1, press 0 Calibrate to clear the            previous curve. Aspirate the standards in numerical order.        -   Press standard number and calibrate for each standard.        -   5) Press Print to print the graph and correlation            coefficient.        -   6) Rerun one or all standards, if necessary. To rerun            Standard 3, aspirate standard and press 3 Calibrate.        -   7) Reslope the standard curve by pressing Reslope after            aspirating the designated reslope standard.    -   D) The correlation coefficient should be greater than or equal        to 0.990.    -   E) Check the calibration curve for drift, accuracy and precision        with standards and controls every 20 samples.        IV) Analysis Procedure    -   A) Autozero with the blank before each standard, control and        sample.    -   B) Aspirate sample and press Read Sample. The software will take        3 readings of absorbance and then average those readings. Wait        until software says idle. Rerun the sample if the standard        deviation is greater than 10% of the sample result.        V) Instrument Shutdown    -   A) Aspirate 5% Hydrochloric Acid (HCl) for 5 minutes and        deionized water for 10 minutes to clean the burner head. Remove        the capillary tube from the water.    -   B) Press Flame On/Off to turn off flame.    -   C) Close air compressor valve.    -   D) Close acetylene cylinder valve.    -   E) Press Bleed Gases to bleed the acetylene gas from the lines.        The cylinder pressure should drop to zero.    -   F) Exit the software, power OFF the AAnalyst 300, and shut down        the computer.

Further, the last 4 columns of Table 8 disclose “Metal PPM (Ionic)”; andO₂ (ppm); NO₃ (ppm); and “pH”. Each of these sets of numbers weredetermined by utilizing an ion selective electrode measurementtechnique. In particular, a NICO ion analyzer was utilized. Precisestabilization times and actual experimental procedures for collectingthe data in each of these three columns of Table 8 (and Table 9) occursimmediately below.

DEFINITIONS

-   -   Stabilization Times—After immersing the electrodes in a new        solution, the mV reading normally falls rapidly at first by        several mV, and then gradually, and increasingly slowly, falls        to a stable reading as the ISE membrane equilibrates and the        reference electrode liquid junction potential stabilizes. This        equilibration may take up to 3 or 4 minutes to reach a        completely stable value. Sometimes the reading begins to rise        again after a short period of stability and it is important to        ensure that the recording is made at the lowest point, before        this rise has proceeded to any great extent. In this study it        was found that it was not necessary to wait for a completely        stable reading but that satisfactory results could be obtained        by taking a reading after a pre-set time, so that each        measurement was made at the same point of the decay curve. For        optimum performance it was found that this delay time should be        at least two minutes to ensure that the reading was in the        shallower part of the curve.        Procedure:    -   1. Get two 150 mL beakers for each electrode to be used        (typically 4). One beaker will be used for the solutions        themselves and the other beaker will be filled with DI H2O to        equalize the membranes of each electrode after each solution has        been tested.    -   2. Obtain approximately 50 mL of the solution of interest for        each electrode being used and its respective beaker. (Commonly        about 200 mL for testing of Ag, NO3, NO2 and pH of a solution.)    -   3. If not already in place, locate and insert each desired ion        selective electrode and its respective reference electrode into        the appropriate receptacle. Only one electrode and its reference        electrode per receptacle unless both ion selective electrodes        require the use of the same reference electrode. Remove caps        from each electrode and its corresponding reference electrode        and place them into the electrode holder.    -   4. Turn on the computer associated with the NICO Ion Analyser        and the software to operate it.    -   5. Open the 8-Channel Ion Electrode Analyser Software to operate        the equipment.    -   6. Each ion selective electrode must be calibrated using the        standards most accurate for our purposes. This calibration must        be done each time the machine is turned on and for most accurate        results, should be calibrated before each individual sample is        tested. For each ion selective electrode, at the present time, 1        ppm, 10 ppm and 100 ppm give the best calibration for our        solutions and their relative readings. Locate the “Calibrate”        button on the software interface and follow the directions.    -   7. Each beaker is to be rinsed with DI H2O and swabbed with a        lint free cloth before each use.    -   8. Fill each “solution” beaker with approximately 50 mL of the        solution of interest and each “equalizer” beaker with        approximately 100 mL of DI H2O.    -   9. Place each electrode into the “equalizer” beakers for        approximately 15 seconds to ensure the membranes are in the same        state and equal before each new solution is tested.    -   10. Remove electrodes from the DI H2O and wipe gently with a        lint free cloth.    -   11. Place the electrodes into the solution so that each        electrode and reference electrode is immersed at least 2 cm.        Gently swirl the electrode and beaker to ensure homogeneity and        good to remove any air bubbles that may be between the        electrodes and the solution.    -   12. Let the electrodes remain undisturbed for 2-5 minutes        depending on the stabilization time for the particular solution.    -   13. When the operator is satisfied with the reading and it        occurs during the stabilization time, it must be recorded using        the software. Upon hitting the “Record” button you will be        prompted for a filename for this specific set of data. Also        record these readings in a lab book that can be used for        transferring numbers to external speadsheets and the like.    -   14. Remove the electrodes from the solution and discard the        solution.    -   15. Rinse each electrode with a stream of DI H2O.    -   16. Rinse each 150 mL beaker with DI H2O.    -   17. Dry both the electrodes and the beakers with lint free        cloths.    -   18. Return each electrode to its holder and replace caps if no        further testing is to occur.

Table 9 is also included herein which contains similar data to that datashown in Table 8 (and discussed in Examples 1-5) with the only exceptionbeing AT-031. The data in Table 9 comes from procedures copied fromExamples 1-5 except that such procedures were conducted at a much laterpoint in time (months apart). The raw materials and associatedsolutions, summarized in Table 9 show that the raw materials, as well assolutions therefrom, are substantially constant. Accordingly, theprocess is very reliable and reproducible.

TABLE 9 Solution Contents Analytical Results Silver % by Zinc % byCopper % by Ag ppm Zn ppm Cu ppm Metal ppm NO2 NO3 ID Constituent VolumeConstituent Volume Constituent Volume (AAS) (AAS) (AAS) Ionic (ppm)(ppm) pH AT-060 AT-060 100.0% 40.9 24.2 N/A 0.00 4.04 AT-031 AT-031100.0% 41.3 23.3 41.3 15 5.23 AT-059 AT-059 100.0% 41.4 10.9 N/A 13.32.98 BT-006 BT-006 100.0% 24 ** N/A 20.8 3.13 CT-006 CT-006 100.0% 9.217.3 5.20 4.38 GR1B GR2B GR3B AT-059 24.2% BT-006 41.7% CT-006 34.2%9.99 9.85 2.91 * N/A 58 3.27 GR4B GR5B AT-031 24.2% BT-006 75.8% 9.3418.8 5.5 N/A 42.8 3.25 GR6B GR7B AT-060 48.9% BT-006 51.1% 20.6 12.7 8.7N/A 30.5 3.38 GR8B AT-060 17.1% BT-006 82.9% 7.13 19.1 5 N/A 39.4 3.2GR9B AT-060 70.0% BT-006 10.0% CT-006 20.0% 29.9 3.7 1.7 * N/A 15.8 3.82GR10B AT-60/31/59 36.4% BT-006 63.6% 14.2 15.6 7 N/A 21.4 3.2 N/A ph isout of testing range * Can not be tested due to silver and copperinteraction ** Zinc can not be tested with deviceScanning Electron Microscopy/EDS

Scanning electron microscopy was performed on each of the new materialsand solutions GR1-GR10 made according to Examples 1-5.

FIGS. 42 a-42 e show EDS results for a scanning electron microscopecorresponding to each of the 5 raw materials made in Examples 1-5,respectively.

FIGS. 42 f-42 o show EDS analysis for each of the 10 solutions shown inTables 8 and 9.

XEDS spectra were obtained using a EDAX Lithium drifted silicon detectorsystem coupled to a IXRF Systems digital processor, which was interfacedwith an AMRAY 1820 SEM with a LaB6 electron gun. Interpretation of allspectra generated was performed using IXRF EDS2008, version 1.0 Rev Edata collection and processing software.

Instrumentation hardware and software setup entails positioning liquidsamples from each Run ID on a sample stage in such a manner within theSEM to permit the area of interest to be under the electron beam forimaging purposes while allowing emitted energies to have optimum path tothe XEDS detector. A sample is typically positioned about 18 mm beneaththe aperture for the final lens and tilted nominally at 18° towards theXEDS detector. All work is accomplished within a vacuum chamber,maintained at about 10⁻⁶ torr.

The final lens aperture is adjusted to 200 to 300 μm in diameter and thebeam spot size is adjusted to achieve an adequate x-ray photon countrate for the digital “pulse” processor. Data collection periods rangebetween 200 and 300 seconds, with “dead-times” of less than 15%.

An aliquot of liquid sample solution is placed onto a AuPd sputteredglass slide followed by a dehydration step which includes freeze dryingthe solution or drying the solution under a dry nitrogen gas flow toyield particulates from the suspension. Due to the nature of theparticulates, no secondary coating is required for either imaging orXEDS analysis.

FIGS. 43 a(i-iv)-43 e(i-iv) disclose photomicrographs, at 4 differentmagnifications each, corresponding to freeze-drying each of thematerials produced in Examples 1-5, as well as freeze drying each of thesolutions GR1-GR10 recorded in Tables 8 and 9. Specifically, FIGS. 43f(i-iv)-43 o(i-iv) correspond to the solutions GR1-GR10, respectively.All of the photomicrographs were generated with an AMRAY 1820 SEM withan LaB6 electron gun. Magnification size lens are shown on eachphotomicrograph.

Transmission Electron Microscopy

Transmission Electron Microscopy was performed on raw materialscorresponding to the components used to manufacture GR5 and GR8, as wellas the solutions GR5 and GR8. Specifically, an additional run wasperformed corresponding to those production parameters associated withmanufacturing AT031 (i.e, the silver constituent in GR5); an additionalrun was performed corresponding to those production parametersassociated with manufacturing AT060 (i.e., the silver constituent inGR8); and an additional run was performed corresponding to thoseproduction parameters associated with manufacturing BT006 (i.e., thezinc constituent used in both GR5 and GR8). The components were thenmixed together in a similar manner as discussed above herein to resultin solutions equivalent to previously manufactured GR5 and GR8.

FIGS. 43 p(i)-43 p(iii) disclose three different magnification TEMphotomicrographs of a silver constituent made corresponding to theproduction parameters used to manufacture AT031.

FIGS. 43 q(i)-43 q(vi) disclose six different TEM photomicrographs takenat three different magnifications of a silver constituent madecorresponding to the production parameters used to manufacture AT060.

FIGS. 43 r(i)-43 r(ii) disclose two different TEM photomicrographs takenat two different magnifications of a zinc constituent made according tothe production parameters used to manufacture BT006.

FIGS. 43 s(i)-43 s(v) disclose five different TEM photomicrographs takenat three different magnifications of a solution GR5.

FIGS. 43 t(i)-43 t(x) disclose ten different TEM photomicrographs takenat three different magnifications of a solution GR8.

The samples for each of the TEM photomicrographs were prepared at roomtemperature. Specifically, 4 microliters of each liquid sample wereplaced onto a holey carbon film which was located on top of filter paper(used to wick off excess liquid). The filter paper was moved to a dryspot and this procedure was repeated resulting in 8 total microliters ofeach liquid sample being contacted with one portion of the holey carbonfilm. The carbon film grids were then mounted in a single tilt holderand placed in the loadlock of the JEOL 2100 CryoTEM to pump for about 15minutes. The sample was then introduced into the column and the TEMmicroscopy work performed.

The JEOL 2100 CryoTEM operated at 200 kv accelerating potential. Imageswere recorded on a Gatan digital camera of ultra high sensitivity.Typical conditions were 50 micron condenser aperture, spot size 2, andalpha 3.

These TEM photomicrographs show clearly that the average particle sizeof those particles in FIG. 43 p (i.e., those corresponding to the silverconstant in GR05) are smaller than those particles shown in FIG. 43 q(i.e., those corresponding to the silver constituent in GR8). Further,crystal planes are clearly shown in both sets of FIGS. 43 p and 43 q.Moreover, FIG. 43 q show the development of distinct crystal facets,some of which correspond to the known 111 cubic structure for silver.

TEM photomicrographs 43 r do not show any significant crystallization ofzinc.

TEM photomicrographs 43 s (corresponding to solution GR5) also showsimilar silver features as shown in FIG. 43 p; and the photomicrographs43 t (i.e., corresponding to solution GR8) also show similar features asshown in FIG. 43 q.

Thus, these TEM photomicrographs suggest that the processing parametersutilized to manufacture GR5 resulted in somewhat smaller silver-basednanoparticles, when compared to those silver-based nanoparticlesassociated with GR8. The primary difference in production parametersbetween GR5 and GR8 was the location of the two adjustable plasmas 4used to make the silver constituents in each solution. The zincconstituents in both of GR5 and GR8 are the same. However, the silverconstituents in GR5 is made by adjustable plasmas 4 located at the FirstElectrode Set and the Fourth Electrode Set; whereas the silverconstituent in GR8 is made by adjustable plasmas 4 located at the Firstand Second Electrode Sets.

UV-VIS Spectroscopy

Energy absorption spectra were obtained using US-VISmicro-spec-photometry. This information was acquired using dual beamscanning monochrometer systems capable of scanning the wavelength rangeof 190 nm to 1100 nm. Two UV-Vis spectrometers were used to collectabsorption spectra; these were a Jasco V530 and a Jasco MSV350.Instrumentation was setup to support measurement of low-concentrationliquid samples using one of a number of fuzed-quartz sample holders or“cuvettes”. The various cuvettes allow data to be collected at 10 min, 1mm or 0.1 mm optic path of sample. Data was acquired over the abovewavelength range using both PMT and LED detectors with the followingparameters; bandwidth of 2 nm, with data pitch of 0.5 nm, with andwithout a water baseline background. Both tungsten “halogen” andHydrogen “D2” energy sources were used as the primary energy sources.Optical paths of these spectrometers were setup to allow the energy beamto pass through the samples with focus towards the center of the samplecuvettes. Sample preparation was limited to filling and capping thecuvettes and then physically placing the samples into the cuvetteholder, within the fully enclosed sample compartment. Optical absorptionof energy by the materials of interest was determined. Data output wasmeasured and displayed as Absorbance Units (per Beer-Lambert's Law)versus wavelength and frequency.

Spectral signatures in a UV-Visible range were obtained for each of theraw materials produced in Examples 1-5 as well as in each of thesolutions GR1-GR10 shown in Tables 8 and 9.

Specifically, FIG. 44 a shows UV-Vis spectral signature of each of the 5raw materials with a wavelength of about 190 nm-600 nm.

FIG. 44 b shows the UV-Vis spectral pattern for each of the 10 solutionsGR1-GR10 for the same wavelength range.

FIG. 44 c shows the UV-Vis spectral pattern of each of the 10 solutionsGR1-GR10 over a range of 190 nm-225 nm.

FIG. 44 d is a UV-Vis spectra of each of the 10 solutions GR1-GR10 overa wavelength of about 240 nm-500 nm.

FIG. 44 e is a UV-Vis spectral pattern for each of the solutionsGR1-GR10 over a wavelength range of about 245 nm-450 nm.

The UV-Vis spectral data for each of FIGS. 44 a-44 e were obtained froma Jasco V-530 UV-Vis Spectrophotometer. Pertinent operational conditionsfor the collection of each UV-Vis spectral pattern are shown in FIGS. 44a-44 e.

In general, UV-Vis spectroscopy is the measurement of the wavelength andintensity of absorption of near-ultraviolet and visible light by asample. Ultraviolet and visible light are energetic enough to promoteouter electrons to higher energy levels. UV-Vis spectroscopy can beapplied to molecules and inorganic ions or complexes in solution.

The UV-Vis spectra have broad features that can be used for sampleidentification but are also useful for quantitative measurements. Theconcentration of an analyte in solution can be determined by measuringthe absorbance at some wavelength and applying the Beer-Lambert Law.

The dual beam UV-Vis spectrophotometer was used to subtract any signalsfrom the solvent (in this case water) in order to specificallycharacterize the samples of interest. In this case the reference is thefeedstock water that has been drawn from the outlet of the ReverseOsmosis process discussed in the Examples section herein.

Raman Spectroscopy

Raman spectral signatures were, obtained using a Renishaw InviaSpectrometer with relevant operating information shown in FIG. 45. Itshould be noted that no significant differences were seen for each ofthe GR1-GR10 blends using Raman Spectroscopy.

The reflection micro-spectrograph with Leica DL DM microscope was fittedwith either a 20× (NA=0.5) water immersion or a 5× (NA=0.12) dry lens.The rear aperture of each lens was sized to equal or exceed the expandedlaser beam diameter. Two laser frequencies were used, these being amultiline 50 mW Argon laser at V2 power setup for 514.5 nm and a 20 mWHeNe laser at 633 nm. High resolution gratings were fitted in themonochrometer optic path which allowed continuous scans from 50 to 4000wavenumbers (1/cm). Ten to 20 second integration times were used. Samplefluid was placed below the lens in a 50 ml beaker. Both lasers were usedto investigate resonance bands, while the former laser was primarilyused to obtain Raman spectra. Sample size was about 25 ml. Measurementsmade with the 5× dry lens were made with the objective positioned about5 mm above the fluid to interrogate a volume about 7 mm beneath thewater meniscus. Immersion measurements were made with the 20× immersionlens positioned about 4 mm into the sample allowing investigation of thesame spatial volume. CCD detector acquisition areas were individuallyadjusted for each lens to maximize signal intensity and signal-to-noiseratios.

Biological Characterization

Bioscreen Results

A Bioscreen C microbiology reader was utilized to compare theeffectiveness of the raw materials made in accordance with Examples 1-5,as well as the 10 solutions GR1-GR10 made therefrom. Specific procedurefor obtaining Bioscreen results follows below.

Bacterial Strains

Escherichia coli was obtained from the American Type Culture Collection(ATCC) under the accession number 25922. The initial pellets werereconstituted in trypticase soy broth (TSB, Becton Dickinson andCompany, Sparks, Md.) and aseptically transferred to a culture flaskcontaining 10 ml of TSB followed by overnight incubation at 37° C. in aForm a 3157 water-jacketed incubator (Thermo Scientific, Waltham, Mass.,USA).

Maintenance and Storage of Bacteria

Bacterial strains were kept on trypticase soy agar (TSA, BectonDickinson and Company, Sparks, Md.) plates and aliquots werecryogenically stored at −80° C. in MicroBank tubes (Pro-LabIncorporated, Ontario, Canada).

Preparation of Bacterial Cultures

Microbank tubes were thawed at room temperature and opened in a NuAireLabgard 440 biological class II safety cabinet (NuAire Inc., Plymouth,Minn., USA). Using a sterile inoculating needle, one microbank bead wasaseptically transferred from the stock tube into 10 ml of eitherTrypticase Soy Broth (TSB, Becton Dickenson and Company, Sparks, Md.)for Bioscreen analysis or Mueller-Hinton Broth (MHB, Becton Dickinsonand Company, Sparks, Md.) for MIC/MLC analysis. Overnight cultures ofbacterial strains were grown at 37° C. for 18 hours in a Form a 3157water-jacketed incubator (Thermo Scientific, Waltham, Mass., USA) anddiluted to a 0.5 McFarland turbidity standard. Subsequently, a 10⁻¹dilution of the McFarland standard was performed, to give an approximatebacterial count of 1.0×10⁷ CFU/ml. This final dilution must be usedwithin 30 minutes of creation to prevent an increase in bacterialdensity due to cellular growth.

Dilution of Nanoparticle Solutions

Nanoparticle solutions were diluted in MHB and sterile dH₂O to a 2×testing concentration yielding a total volume of 1.5 ml. Of this volume,7501 consisted of MHB, while the other 750 μl consisted of varyingamounts of sterile dH₂O and the nanoparticle solution to make a 2×concentration of the particular nanoparticle solution being tested.Testing dilutions (final concentration in reaction) ranged from 0.5 ppmAg to 6.0 ppm Ag nanoparticle concentration with testing performed atevery 0.5 ppm interval.

Preparation of Bioscreen Reaction

To determine the minimum inhibitory concentration (MIC) of nanoparticlesolutions, 100 μl of the diluted bacterial culture was added to 100 μlof a particular nanoparticle solution at the desired testingconcentration in the separate, sterile wells of a 100 well microtiterplate (Growth Curves USA, Piscataway, N.J., USA). Wells inoculated withboth 100 μl of the diluted bacterial culture and 100 μl of a 1:1MHB/sterile ddH₂O mix served as positive controls, while wells with 100μl of MHB and 100 μl of a 1:1 MHB/sterile ddH₂O mix served as negativecontrols for the reaction. Plates were placed inside the tray of aBioscreen C Microbiology Reader (Growth Curves USA, Piscataway, N.J.,USA) and incubated at a constant 37° C. for 15 hours with opticaldensity (O.D.) measurements being taken every 10 minutes. Before eachO.D. measurement, plates were automatically shaken for 10 seconds atmedium intensity to prevent settling of bacteria and to ensure ahomogenous reaction well.

Determination of Both MIC and MLC

All data was collected using EZExperiment Software (Growth Curves USA,Piscataway, N.J., USA) and analyzed using Microsoft Excel (MicrosoftCorporation, Redmond, Wash., USA). The growth curves of bacteria strainstreated with different nanoparticle solutions were constructed and theMIC determined. The MIC was defined as the lowest concentration ofnanoparticle solution that prevented the growth of the bacterial culturefor 15 hours, as measured by optical density using the Bioscreen CMicrobiology Reader.

Once the MIC was determined, the test medium from the MIC and subsequenthigher concentrations was removed from each well and combined accordingto concentration in appropriately labeled, sterile Eppendorf tubes. TSAplates were inoculated with 100 μl of test medium and incubatedovernight at 37° C. in a Form a 3157 water-jacketed incubator (ThermoScientific, Waltham, Mass., USA). The minimum lethal concentration (MLC)was defined as the lowest concentration of nanoparticle solution thatprevented the growth of the bacterial culture as measured by colonygrowth on TSA.

The results of the Bioscreen runs are shown in FIG. 46. It should benoted that the raw materials AT031; AT059 and AT060 had reasonableperformance, whereas the raw materials BT-006 and CT-006 did not slowdown growth of the E. coli at all. In this regard, the longer a curveremains at low optical density (“OD”) the better the performance againstbacteria.

In contrast, each of the solutions GR1-GR10 showed superior performance,relative to each of the raw materials AT031, AT060 and AT059.Interestingly, the combination of the raw materials associated withsilver nanoparticles with those raw materials associated with both zincand copper nanoparticles produced unexpected synergistic results.

Additional Bioscreen results are shown in FIGS. 47 and 48. Data reportedin these Figures are known as “MIC” data. “MIC” stands for minimuminhibitory concentration. MIC data was only generated for GR3 and GR8.It is clear from reviewing the data in each of FIGS. 47 and 48 thatappropriate MIC values for GR3 and GR8 were around 2-3 ppm

Due to the unexpected favorable results shown in FIG. 46, the sequentialaddition of the raw material BT-006, made in accordance with Example 4,was added to the raw material AT-060 made in accordance with Example 2(i.e., a zinc-based nanoparticle solution was added to a silver- basednanoparticle solution. The amount of silver present (as determined byatomic absorption spectroscopy) was maintained at 1ppm. The amount ofBT-006 in the nanoparticle solution added thereto is reported in FIG.49. It is interesting to note that enhanced antimicrobial performanceagainst E. coli was achieved with increasing amounts of zincnanoparticle solutions, i.e., BT-006, (from Example 4) being addedthereto. Further, Figures 50 a-50 d show additional Bioscreeninformation showing performance against e. coli by adding a conditionedwater (“GZA”) to the nanoparticle solution AT-060 from Example 2.

GZA raw material was made in a manner similar to the BT-006 raw materialexcept that a platinum electrode 1/5 configuration was utilized ratherthan zinc.

Freeze-Drying

FIG. 54 shows another set of Bioscreen results whereby solutionsreferred to in Tables 8 and 9 herein as GR5 and GR8, were compared forefficacy against E. coli, as well as the same solutions having beenfirst completely freeze-dried and thereafter rehydrated with water(liquid 3) such rehydration being effected to result in the sameoriginal ppm.

Freeze-drying was accomplished by placing the GR5 and GR8 solution in aplastic (nalgene) container and placing the plastic container in aBenchTop 2K freeze dryer (manufactured by Virtis) which was maintainedat a temperature of about −52° C. and a vaccuum of less than 100mililiter. About 10-20 ml of solution will freeze-dry overnight.

As is shown in FIG. 54, the performance of freeze-dried and rehydratednanoparticles is identical to the performance of the original GR5 andGR8 solutions.

Viability/Cytoxicity Testing of Mammalian Cells

The following procedures were utilized to obtain cell viability and/orcytotoxicity measurements.

Cell Lines

Mus musculus (mouse) liver epithelial cells (accession number CRL-1638)and Sus scrofa domesticus (minipig) kidney fibrobast cells (accessionnumber CCL-166) were obtained from the American Type Culture Collection(ATCC).

Cell Culturing from Frozen Stocks

Cell lines were thawed by gentle agitation in a Napco 203 water bath(Thermo Scientific, Waltham, Mass., USA) at 37° C. for 2 minutes. Toreduce microbial contamination, the cap and O-ring of the frozen culturevial were kept above the water level during thawing. As soon as thecontents of the culture vial were thawed, the vial was removed from thewater, sprayed with 95% ethanol, and transferred into a NuAire Labgard440 biological class II safety cabinet (NuAire Inc., Plymouth, Minn.,USA). The vial contents were then transferred to a sterile 75 cm² tissueculture flask (Corning Life Sciences, Lowell, Mass., USA) and dilutedwith the recommended amount of complete culture medium. Murine liverepithelial cell line CRL-1638 required propagation in complete culturemedia composed of 90% Dulbecco's Modified Eagle's Medium (ATCC,Manassas, Va., USA) and 10% fetal bovine serum (ATCC, Manassas, Va.,USA), while minipig kidney fibroblast cell line CCL-166 was grown incomplete culture media comprised of 80% Dulbecco's Modified Eagle'sMedium and 20% fetal bovine serum. Cell line CRL-1638 was diluted withgrowth media in a 1:15 ratio, while cell line CCL-166 was diluted withgrowth media in a 1:10 ratio. The culture flasks were then incubated atabout 37° C., utilizing a 5% CO₂ and 95% humidified atmosphere in aNuAire, IR Autoflow water-jacketed, CO₂ incubator (NuAire Inc.,Plymouth, Minn., USA).

Medium Renewal and Care of Growing Cells

Every two days, old growth medium was removed from culturing flasks andreplaced with fresh growth medium. Each day, observations for microbialgrowth, such as fungal colonies and turbidity in medium, were made withthe naked eye. Additionally, cultured cells were observed under aninverted phase contrast microscope (VWR Vistavision, VWR International,and West Chester, Pa., USA) to check for both general health of thecells and cell confluency.

Subculturing of Cells

Once cells reached approximately 80% confluent growth, cells were deemedready for subculturing. Old growth medium was removed and discarded andthe cell sheet rinsed with 5 ml of prewarmed trypsin-EDTA dissociatingsolution (ATCC, Manassas, Va., USA). After 30 seconds of contact withthe cell sheet, the trypsin-EDTA was removed and discarded. Ensuringthat both the entire cell monolayer was covered and the flask was notagitated, a 3 ml volume of the prewarmed trypsin-EDTA solution was addedto the cell sheet followed by incubation of the culture flask at 37° C.for about 15 minutes. After cell dissociation, trypsin-EDTA wasinactivated by adding about 6 ml of complete growth medium to the cellculture flask followed by gentle pipetting to aspirate cells.

In order to count cells, 200 μl of the cell suspension was collected ina 15 ml centrifuge tube (Corning Life Sciences, Lowell, Mass., USA).Both 300 μL of phosphate buffered saline (ATCC, Manassas, Va., USA) and500 μL of a 0.4% trypan blue solution (ATCC, Manassas, Va., USA) wasadded to the collected cell suspension and mixed thoroughly. Afterallowing to stand for about 15 minutes, 10 μl of the mixture was placedin each chamber of an iN Cyto, C-Chip disposable hemacytometer (INCYTO,Seoul, Korea) where the cells were counted with a VWR Vistavisioninverted phase contrast microscope (VWR International, West Chester,Pa., USA) according to the manufacturer's instructions. Theconcentration of the cells in the suspension was calculated using aconversion formula based upon the cell count obtained from thehemacytometer.

Cytotoxicity Testing

The wells of black, clear bottom, cell culture-treated microtiter plates(Corning Life Sciences, Lowell, Mass., USA) were seeded with 200 μl ofculture medium containing approximately 1.7×10⁴ cells as shown inFIG. 1. Cells were allowed to equilibrate in the microtiter plates atabout 37° C., utilizing a 5% CO₂ and 95% humidified atmosphere for about48 hours. After the equilibration period, culture medium was removedfrom each well and replaced with 100 μl of fresh growth medium in allwells except for those in column 3 of the plate. A 100 volume of freshmedium supplemented with 2× of the desired testing concentration ofHydronanon™ solution was placed in each well as shown in Table 10.

TABLE 10

Microwell plate setup for cytotoxicity testing. All outer wells (shadedarea) of the plate contained only 200 μl of culture medium (no cells) toact as a blank vehicle control (VCb) for the experiment. As a positivevehicle control, wells 2B-2G (VC1) and wells 11B-11G (VC2) were seededwith both culture medium and cells. One Hydronanon ™ solution was testedon each plate (H_(x)). The highest concentration of Hydronanon ™solution was placed in wells 3B-3D (C₁), while seven, 20% dilutions(C₂-C₇) of each solution were present in each consecutive well.

Microtiter plates were incubated with the treatment compounds 37° C.,utilizing a 5% CO₂ and 95% humidified atmosphere for 24 hours. Afterincubation with nanoparticle solutions, the culture medium was removedand discarded from each well and replaced with 100 μl of fresh mediacontaining Alamar Blue™ (Biosource International, Camarillo, Calif.,USA) at a concentration of 50 μl dye/ml media. Plates were gently shakenby hand for about 10 seconds and incubated at about 37° C., utilizing a5% CO₂ and 95% humidified atmosphere for 2.5 hours. Fluorescence wasthen measured in each well utilizing an excitation wavelength of 544 nmand an emission wavelength of 590 nm. Fluorescence measurements werecarried out on the Fluoroskan II fluorometer produced by Labsystems(Thermo Scientific, Waltham, Mass., USA).

Data Analysis

Cytotoxicity of the nanoparticle solutions was determined by measuringthe proportion of viable cells after treatment when compared to thenon-treated control cells. A percent viability of cells after treatmentwas then calculated and used to generate the concentration ofnanoparticle at which fifty percent of cellular death occurred (LC₅₀).All data was analyzed using GraphPad Prism software (GraphPad SoftwareInc., San Diego, Calif., USA).

Results of the viability/cytotoxicity tests are shown in Figures areshown in FIGS. 51 a-51 h; 52 a-52 f; and FIGS. 53 a-53 h.

With regard to FIGS. 51 a and 51 b, the performance of solution “GR3”was tested against both mini-pig kidney fibroblast cells (FIG. 51 a) andmurine liver epithelial cells (FIG. 51 b).

Similarly, FIGS. 51 c and 51 d tested the performance of GR5 againstkidney cells and murine liver cells, respectively; FIGS. 51 e and 51 ftested the performance of GR8 against kidney cells and liver cells,respectively; and FIGS. 51 g and 51 h tested the performance of GR9against kidney cells and liver cells, respectively.

In each of FIGS. 51 a-51 h, a biphasic response is noted. A biphasicresponse occurred at different concentrations for each solution and setof cells, however, the general trend or each solution tested showed thata certain concentration of nanoparticles produced according to theembodiments disclosed herein exhibited enhanced growth rates for each ofthe kidney and liver cells, relative to control. In this regard, anyportion of any of the curves that are vertically above the dotted linecorresponding to 100% (i.e., control) had a higher fluorometer readingfrom the generated flourenscence discussed above herein. Accordingly, itis clear that particles and/or nanoparticle solutions made according tothe present invention can have an enhanced growth rate effect onmammalian cells including at least, kidney and liver cells.

FIGS. 52 a-52 f tested a narrower response range of both silvernanoparticle concentrations and total nanoparticle concentrations. Thevalues “LD₅₀” reported for each of the solutions 3, 5 and 8 in each ofFIGS. 52 ab, 52 cd, and 52 ef, respectively, correspond to the parts permillion of silver-based nanoparticles (FIGS. 52 a, c and e) and totalnanoparticle parts per million (corresponding to FIGS. 52 b, d and f).With regard to the silver nanoparticle concentration, it is clear thatLD₅₀'s range between about 2.5 to about 5.4. In contrast, the LD₅₀'s forthe total nanoparticle solutions vary from about 6 to about 16.

With regard to FIG. 53 a-53 h, “LD₅₀” measurements were made for eachsolution GR3, GR5, GR8 and GR9 against mini-pig kidney fibroblast cells.As shown in each of these Figures, the “LD₅₀” values for totalnanoparticles present ranged from a low of about 4.3 for GR9 to a highof about 10.5-11 for each of GR5 and GR8.

Example 6 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT098, AT099 and AT100 Without the Use of any Plasmas

This Example utilizes the same basic apparatus used to make thesolutions of Examples 1-5. However, this Example does not utilize anyelectrode(s) 5. This Example utilizes 99.95% pure silver electrodes foreach electrode 1. Tables 11a, 11b and 11c summarize portions ofelectrode design, configuration, location and operating voltages. Asshown in Tables 11a, 11b and 11c, the target voltages were set to a lowof about 2,750 volts in Electrode Set #8 and to a high of about 4,500volts in Electrode Sets #1-3. The high of 4,500 volts essentiallycorresponds to an open circuit which is due to the minimal conductivityof the liquid 3 between each electrode 1, 1′ in Electrode Sets #1-3

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 55 a, 55 b and 55 c.Accordingly, the data contained in Tables 11a, 11b and 11c, as well asFIGS. 55 a, 55 b and 55 c, give a complete understanding of theelectrode design in each electrode set as well as the target and actualvoltages applied to each electrode for the inventive manufacturingprocess. To maintain consistency with the reported electrodeconfigurations of Examples 1-5, space for eight sets of electrodes havebeen included in each of, Tables 11a, 11b and 11c, even though Run ID“AT100” was the only run that actually used eight sets of electrodes.

TABLE 11a Run ID: AT098 Flow Rate: 200 ml/min Target Voltage DistanceDistance Average Set # Electrode # (kV) “c-c” in/mm “x” in/mm Voltage(kV)  7/177.8* 1 5a 4.54 N/A 4.54 5a′ 4.52 N/A 4.51 65/1651** N/A N/AN/A N/A N/A N/A N/A Output Water Temperature 24 C. *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

TABLE 11b Run ID: AT099 Flow Rate: 200 ml/min Target Voltage DistanceDistance Average Set # Electrode # (kV) “c-c” in/mm “x” in/mm Voltage(kV)  7/177.8* 1 5a 4.54 N/A 4.53 5a′ 4.52 N/A 4.49  8/203.2 2 5b 4.55N/A 4.56 5b′ 4.51 N/A 4.52 57/1447.8** N/A N/A N/A N/A N/A N/A OutputWater Temperature 24 C. *Distance from water inlet to center of firstelectrode set **Distance from center of last electrode set to wateroutlet

TABLE 11c Run ID: AT100 Flow Rate: 200 ml/min Target Voltage DistanceDistance Average Set # Electrode # (kV) “c-c” in/mm “x” in/mm Voltage(kV) 7/177.8* 1 5a 4.53 N/A 4.53 5a′ 4.49 N/A 4.49 8/203.2 2 5b 4.51 N/A4.51 5b′ 4.48 N/A 4.47 8/203.2 3 5c 4.52 N/A 4.52 5c′ 4.45 N/A 4.458/203.2 4 5d 4.40 N/A 4.40 5d′ 4.32 N/A 4.32 9/228.6 5 5e 4.38 N/A 4.375e′ 4.27 N/A 4.26 8/203.2 6 5f 3.85 N/A 3.80 5f′ 3.71 N/A 3.65 8/203.2 75g 3.55 N/A 3.43 5g′ 3.30 N/A 3.23 8/203.2 8 5h 2.79 N/A 2.76 5h′ 2.75N/A 2.69 8/203.2** Output Water Temperature 82 C. *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained. Slight process modifications wereincorporated into those AAS procedures discussed earlier herein. Theseprocess changes are incorporated immediately below.

The AAS values were obtained from a Perkin Elmer AAnalyst 300Spectrometer system, as in Examples 1-5. The samples manufactured inaccordance with Examples 6-12 were prepared by adding a small amount ofnitric acid or hydrochloric acid (usually 2-4% of final volume) and thendilution to a desirable characteristic concentration range or linearrange of the specific element to improve accuracy of the result. The“desirable” range is an order of magnitude estimate based on productionparameters established during product development. For pure metalsanalysis, a known amount of feedstock material is digested in a knownamount of acid and diluted to ensure that the signal strength of theabsorbance will be within the tolerance limits and more specifically themost accurate range of the detector settings, better known as the linearrange.

The specific operating procedure for the Perkin Elmer AAnalyst 300system is as follows:

I) Principle

-   -   The Perkin Elmer AAnalyst 300 system consists of a high        efficiency burner system, with either a sapphire GemTip or        stainless steel beaded nebulizer and an atomic absorption        spectrometer. The burner system provides the thermal energy        necessary to dissociate the chemical compounds, providing free        analyte atoms so that atomic absorption occurs. The spectrometer        measures the amount of light absorbed at a specific wavelength        using a hollow cathode lamp as the primary light source, a        monochromator and a detector. A deuterium arc lamp corrects for        background absorbance caused by non-atomic species in the atom        cloud.        II) Instrument Setup    -   A) Empty waste container to mark. Add deionized water to drain        tubing to ensure that water is present in the drain system float        assembly.    -   B) Ensure that the appropriate Hollow Cathode Lamp for the        analyte to be analyzed is properly installed in the turret.    -   C) Power AAnalyst 300 and computer ON.    -   D) After the AAnalyst 300 has warmed up for a minimum of 30        minutes, start the AAWin Analyst software    -   E) Recall Method to be analyzed.    -   F) Ensure that the correct Default Conditions are entered.    -   G) Align the Hollow Cathode Lamp.        -   1) Allow HCL's to warm and stabilize for a minimum of 15            minutes.        -   2) Check that a proper peak and energy level has been            established for the specific lamp.        -   3) Adjust the power and frequency of the lamp settings to            obtain maximum energy.    -   H) Store Method changes in Parameter Entry, Option, Store and #.    -   I) Adjust Burner height.        -   1) Place a white sheet of paper behind the burner to confirm            the location of the light beam.        -   2) Lower the burner head below the light beam with the            vertical adjustment knob.        -   3) Press Cont (Continuous) to display an absorbance value.        -   4) Press A/Z to Autozero.        -   5) Raise the burner head with the vertical adjustment knob            until the display indicates a slight absorbance (0.002).            Slowly lower the head until the display returns to zero.            Lower the head an additional quarter turn to complete the            adjustment.    -   J) Ignite flame.        -   1) Open air compressor valve. Set pressure to 50 to 65 psi.        -   2) Open acetylene gas cylinder valve. Set output pressure to            12 to 14 psi. Replace cylinder when pressure falls to 75 psi            to prevent valve and tubing damage from the presence of            acetone.        -   3) Press Gases On/Off. Adjust oxidant flow to 4 Units.        -   4) Press Gases On/Off. Adjust acetylene gas flow to 2 Units.        -   5) Press Flame On/Off to turn flame on.            -   Note: Do not directly view the lamp or flame without                protective ultraviolet radiation eyewear.    -   K) Aspirate deionized water through the burner head to fully        warm the burner head for 3 to 5 minutes.    -   L) Adjust Burner Position and Nebulizer.        -   1) Aspirate a standard with a signal of approximately            0.2-0.5 absorbance units.        -   2) Obtain maximum burner position absorbance by rotating the            horizontal, vertical and rotational adjustment knobs.        -   3) Loosen the nebulizer locking ring by turning it            clockwise. Slowly turn the nebulizer adjustment knob to            obtain maximum absorbance. Lock the knob in place with the            locking ring.        -   Note: An element, such as Silver, which is at a wavelength            where gases do not absorb is optimal for adjusting the            Burner and Nebulizer.            III) Calibration Procedure    -   A) Calibrate with standards that bracket the sample        concentrations.    -   B) WinAA Analyst software will automatically create a        calibration curve for your sample readings. But check to ensure        that proper absorption is established with each calibration        standard.    -   C) Enter Standard Concentration Values in the Default Conditions        to calculate an AAnalyst 300 standard curve.        -   1) Enter the concentration of the lowest standard for STD1            using significant digits.        -   2) Enter the concentrations of the other standards of the            calibration curve in ascending order and the concentration            of the reslope standard.        -   3) Autozero with the blank before acquiring calibration            values.        -   4) Aspirate Standard 1, press 0 Calibrate to clear the            previous curve. Aspirate the standards in numerical order.        -   Press standard number and calibrate for each standard.        -   5) Press Print to print the graph and correlation            coefficient.        -   6) Rerun one or all standards, if necessary. To rerun            Standard 3, aspirate standard and press 3 Calibrate.    -   D) The correlation coefficient should be greater than or equal        to 0.990.    -   E) Check the calibration curve for drift, accuracy and precision        with calibration standards continuously during operation, at        minimum, one every 20 samples.        IV) Analysis Procedure    -   A) Samples are measured in triplicate using a minimum of 3        replicates per sample.    -   B) Aspirate sample and press Read Sample. The software will take        3 readings of absorbance and then average those readings. Wait        until software says idle. Rerun the sample if the standard        deviation is greater than 50% of the sample result.        V) Instrument Shutdown    -   A) Aspirate 2% Nitric Acid (HNO₃) for 1-3 minutes and deionized        water for 3-5 minutes to clean the burner head. Remove the        capillary tube from the water and run burner-head dry for about        1 minute.    -   B) Press Flame On/Off to turn off flame.    -   C) Close air compressor valve.    -   D) Close acetylene cylinder valve.    -   E) Press Bleed Gases to bleed the acetylene gas from the lines.        The cylinder pressure should drop to zero.    -   F) Exit the software, power OFF the AAnalyst 300, and shut down        the computer.

TABLE 11d Run ID Electrode Configuration Measured PPM AT098 0XXXXXXXBelow Detectable Limit AT099 00XXXXXX Less Than 0.2 PPM AT100 000000007.1 PPM

Table 11d shows the results obtained from Example 6. Table 11d containsa column entitled “Electrode Configuration”. This column containscharacters “0” and “X”. The character “0” corresponds to one electrodeset 5, 5′. The character “X” represents that no electrodes were present.Thus, for Run ID “AT098”, only a single electrode set 5 a, 5 a′ wasutilized. No detectable amount of silver was measurable by the AAStechniques disclosed herein. Run ID “AT099” utilized two electrode sets5 a, 5 a′ and 5 b, 5 b′. The AAS techniques detected some amount ofsilver as being present, but that amount was less than 0.2 ppm. Run ID“AT100” utilized eight electrode sets, 5, 5′. This configurationresulted in a measured ppm of 7.1 ppm. Accordingly, it is possible toobtain metallic-based constituents (e.g., metallic-basednanoparticles/nanoparticle solution) without the use of an electrode 1(and an associated plasma 4). However, the rate of formation ofmetallic-based constituents is much less than that rate obtained byusing one or more plasmas 4. For example, Examples 1-3 disclosedsilver-based products associated with Run ID's AT031, AT036 and AT038.Each of those Run ID's utilized two electrode sets that includedadjustable plasmas 4. The measured silver ppm for each of these sampleswas greater than 40 ppm, which is 5-6 times more than what was measuredin the product made according to Run ID AT100 in this Example 6. Thus,while it is possible to manufacture metallic-based constituents withoutthe use of at least one adjustable plasma 4 (according to the teachingsherein) the rates of formation of metallic based constituents aregreatly reduced when no plasmas 4 are utilized as part of the productiontechniques.

Accordingly, even though eight electrode sets 5, 5 were utilized to makethe product associated with Run AT100, the lack of any electrode setsincluding at least one electrode 1 (i.e., the lack of plasma 4),severely limited the ppm content of silver in the solution produced.

Example 7 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT080, AT081, AT082, AT083, AT084, AT085, AT086 and AT097Using Only a Single Plasma

This Example utilizes the same basic apparatus used to make thesolutions of Examples 1-5, however, this Example uses only a singleplasma 4. Specifically, for Electrode Set #1, this Example uses a “1a,5a” electrode configuration. Subsequent Electrode Sets #2-#8 aresequentially added. Each of Electrode Sets #2-#8 have a “5, 5′”electrode configuration. This Example also utilizes 99.95% pure silverelectrodes for each of electrodes 1 and 5 in each Electrode Set.

Tables 12a-12h summarize portions of electrode design, configuration,location and operating voltages. As shown in Tables 12a-12h, the targetvoltages were set to a low of about 900 volts (at Electrode Set #8) anda high of about 2,300 volts (at Electrode Set #1).

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 56 a, 56 b, 56 c, 56 d, 56 e,56 f, 56 g and 56 h. Accordingly, the data contained in Tables 12a-12h,as well as FIGS. 56 a, 56 b, 56 c, 56 d, 56 e, 56 f, 56 g and 56 h, givea complete understanding of the electrode design in each electrode setas well as the target and actual voltages applied to each electrode forthe manufacturing processes. To maintain consistency with the reportedelectrode configurations of Examples 1-5, space for eight sets ofelectrodes have been included in each in each of Tables 12a, 12b, 12c,12d, 12e, 12f, 12g and 12h even though Run ID “AT080” was the only runthat actually used eight sets of electrodes.

TABLE 12a Run ID: AT097 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 1.78 .26/6.8 1.79 5a 1.82 N/A 1.79 65/1651** N/A N/AN/A N/A N/A N/A N/A Output Water Temperature 35 C. *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

TABLE 12b Run ID: AT086 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.18 .26/6.8 2.15 5a 1.63 N/A 1.67  8/203.2 2 5b1.05 N/A 1.05 5b′ 1.39 N/A 1.43 57/1447.8** N/A N/A N/A N/A N/A N/AOutput Water Temperature 38 C. *Distance from water inlet to center offirst electrode set **Distance from center of last electrode set towater outlet

TABLE 12c Run ID: AT085 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.24 .26/6.8 2.19 5a 1.79 N/A 1.79  8/203.2 2 5b1.16 N/A 1.16 5b′ 1.24 N/A 1.23  8/203.2 3 5c 1.12 N/A 1.14 5c′ 1.34 N/A1.35 49/1244.6** N/A N/A N/A N/A N/A Output Water Temperature 43 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 12d Run ID: AT084 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.29 .26/6.8 2.25 5a 1.95 N/A 1.94 8/203.2 2 5b 1.27N/A 1.26 5b′ 1.39 N/A 1.39 8/203.2 3 5c 1.35 N/A 1.34 5c′ 1.26 N/A 1.258/203.2 4 5d 1.31 N/A 1.32 5d′ 1.59 N/A 1.56  41/1041.4** N/A N/A N/AN/A Output Water Temperature 49 C. *Distance from water inlet to centerof first electrode set **Distance from center of last electrode set towater outlet

TABLE 12e Run ID: AT083 FlowRate: 200 ml/min Target Distance AverageVoltage “c-c” Distance Voltage Set # Electrode # (kV) in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.17 .26/6.8 2.16 5a 1.72 N/A 1.74 8/203.2 2 5b 1.10N/A 1.12 5b′ 1.32 N/A 1.34 8/203.2 3 5c 1.25 N/A 1.24 5c′ 1.12 N/A 1.138/203.2 4 5d 1.31 N/A 1.29 5d′ 1.32 N/A 1.33 9/228.6 5 5e 1.63 N/A 1.645e′ 1.52 N/A 1.52  32/812.8** N/A N/A N/A Output Water Temperature 56 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 12f Run ID: AT082 Flow Rate: 200 ml/min Target Distance AverageVoltage “c-c” Distance Voltage Set # Electrode # (kV) in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.18 .26/6.8 2.17 5a 1.76 N/A 1.75 8/203.2 2 5b 1.08N/A 1.09 5b′ 1.31 N/A 1.32 8/203.2 3 5c 1.26 N/A 1.26 5c′ 1.09 N/A 1.088/203.2 4 5d 1.28 N/A 1.27 5d′ 1.25 N/A 1.22 9/228.6 5 5e 1.60 N/A 1.605e′ 1.17 N/A 1.17 8/203.2 6 5f 0.99 N/A 0.98 5f′ 1.19 N/A 1.18 24/609.6** N/A N/A Output Water Temperature 63 C. *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

TABLE 12g Run ID: AT081 Flow Rate: 200 ml/min Target Distance AverageVoltage “c-c” Distance Voltage Set # Electrode # (kV) in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.23 .26/6.8 2.18 5a 1.77 N/A 1.79 8/203.2 2 5b 1.09N/A 1.09 5b′ 1.30 N/A 1.28 8/203.2 3 5c 1.22 N/A 1.21 5c′ 1.07 N/A 1.078/203.2 4 5d 1.27 N/A 1.27 5d′ 1.21 N/A 1.21 9/228.6 5 5e 1.60 N/A 1.585e′ 1.26 N/A 1.23 8/203.2 6 5f 1.10 N/A 1.09 5f′ 1.02 N/A 0.99 8/203.2 75g 1.14 N/A 1.11 5g′ 1.34 N/A 1.32  16/406.4** N/A Output WaterTemperature 72 C. *Distance from water inlet to center of firstelectrode set **Distance from center of last electrode set to wateroutlet

TABLE 12h Run ID: AT080 Flow Rate: 200 ml/min Target Distance AverageVoltage “c-c” Distance Voltage Set # Electrode # (kV) in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.11 .26/6.8 2.13 5a 1.72 N/A 1.73 8/203.2 2 5b 1.00N/A 1.00 5b′ 1.23 N/A 1.24 8/203.2 3 5c 1.16 N/A 1.16 5c′ 0.97 N/A 0.988/203.2 4 5d 1.15 N/A 1.17 5d′ 1.14 N/A 1.14 9/228.6 5 5e 1.47 N/A 1.495e′ 1.16 N/A 1.16 8/203.2 6 5f 1.02 N/A 1.02 5f′ 0.98 N/A 0.98 8/203.2 75g 1.06 N/A 1.07 5g′ 0.94 N/A 0.96 8/203.2 8 5h 0.92 N/A 0.93 5h′ 1.12N/A 1.14  8/203.2** Output Water Temperature 82 C. *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 12ishows the results. Note that Table 12i includes a column entitled“Electrode Configuration”. This column contains characters of “1” and“0” and “X”. The “1's” represent an electrode configurationcorresponding to Electrode Set #1 (i.e., a 1, 5 combination). The “0's”represent an electrode combination of 5, 5′. The character “X”represents that no electrodes were present. Thus, for example, “AT084”is represented by “1000XXXX” which means a four electrode setcombination was used to make “AT084” and the combination corresponded toSet #1=1, 5; Set #2=5, 5; Set #3=5, 5 and Set #4=5, 5 (there were noSets after Set #4, as represented by “XXXX”).

TABLE 12i Average Particle Electrode Measured Ag Measured Ag SizeDiameter Run ID Configuration PPM (initial) PPM (10 days) Range(Initial) AT097 1XXXXXXX  6.5  6.5   2 nm AT086 10XXXXXX 14.9 13.4  3-7nm AT085 100XXXXX 19.2 18.4  3-8 nm AT084 1000XXXX 24.1 22.9  4-8 nmAT083 10000XXX 30.4 28.1 6-15 nm AT082 100000XX 34.2 27.4 20-100 nm  AT081 1000000X 36.7 29.3 40-120 nm  AT080 10000000 40.9 31.6 40-150 nm 

Table 12i includes a column entitled “Measured Ag PPM (initial)”. Thiscolumn corresponds to the silver content of each of the eight solutionsmeasured within one hour of its production. As shown, the measured ppmincreases with each added Electrode Set, wherein the Run AT080 producesa ppm level for silver comparable in amount to Run ID AT031 of Example3. However, another column entitled, “Measured Ag PPM (10 days)” showsdata which tells another story. Specifically, the “initial” and “10 day”PPM measurements are essentially the same (e.g., within operation errorof the AAS) for samples corresponding to Run Id's AT097, AT086, AT085,AT084 and AT083. This means that essentially no significant settling ofthe constituent particles found in five of the eight runs occurred.However, once samples associated with Run ID AT082, AT081 and AT080 wereexamined after 10 days, a significant portion of the constituentparticles had settled, with samples taken from Run AT080 losing about 10ppm out of 40 ppm due to particulate settling.

In order to obtain an idea of what particle sizes were being produced ineach of the eight samples associated with this Example 7, a dynamiclight scattering (DLS) approach was utilized. Specifically, dynamiclight scattering methods utilizing variations of scattered lightintensities from an LED laser were measured over time to determine anychanges in intensity from particle motion due to Brownian Motion. Theinstrument used to perform these measurements was a VISCOTEK 802 DLSwith Dual Alternating Technology (D.A.T.).

All measurements were made using a 12 μL quartz cell, which was placedinto a temperature controlled cell block. One 827.4 nm laser beam waspassed through the solution to be measured. Scattering intensities weremeasured using a CCD detector with an optical view path mountedtransversely to that of the laser. Experimental data was thenmathematically transformed using variation of Einstein-Stokes andRayleigh equations to derive values representative of particle size anddistribution information. Data collection and math transforms wereperformed using Viscotek Omnisize version 3,0,0,291 software. Thisinstrument hardware and software reliably provides measurements forparticles with a radius from 0.8 nm to 2 μm.

This technique works best when the solution is free of micro-bubbles andparticles subject to Stokes settling motion (some of which was clearlyoccurring in at least three of the samples in this Example 7). Allvessels used to contain and prepare materials to be tested were rinsedand blow-dried to remove any debris. All water used to prepare vesselsand samples was doubly deionized and 0.2 μm filtered. If solvent isneeded, use only spectrographic grade isopropyl alcohol. All were rinsedwith clean water after solvent exposure, and wiped only with cleanlint-free cotton cloth.

An aliquot of solution sample, about 3 ml in total volume, was drawninto a small syringe and then dispensed into a clean about 4 dram glasssample vial. Two (2) syringe filters (0.45 μm) were fixed onto thesyringe during this operation to doubly filter the sample, thus removingany large particles not intended as part of the solution. This samplewas placed into a small vacuum chamber, where it was subjected to a 1minute exposure to a low-level vacuum (<29.5 inches Hg) to boil thesuspension, removing suspended micro-bubbles. The vacuum was drawnthrough a small dual-stage rotary vacuum pump such as a Varian SD-40.Using a glass Tuberculin syringe with a 20 gage or smaller bluntedneedle, sample was withdrawn to fill the syringe and then rinsed, thenplaced into the 12 μL sample cell/cuvette. Additional like-type syringeswere used to withdraw used sample and rinse fluids from this cell. Thefilled cuvette was inspected for obvious entrapped bubbles within theoptical path.

This cell was inserted into the holder located in the VISCOTEK 802 DLS.Prior to this step, the instrument was allowed to fully warm tooperating temperature for about 30 minutes and operating “OmniSIZE”software loaded in the controlling computer. This software willcommunicate and set-up the instrument to manufacturer prescribedconditions. Select a “new” measurement. Validate that the correct samplemeasurement parameters are selected, i.e.; temperature of 40° C.,“Target” laser attenuation value of 300 k counts per second, 3 secondmeasurement duration, water as the solvent, spike and drift respectivelyat 20% and 15%. Correct if needed. Then select “Tools-Options” from thecontrolling menu bar. Insure proper options are annotated; i.e.resolution at 200, ignore first 2 data points, peak reporting thresholdof 0 and 256 correlator channels.

Once the sample was placed into the holder, the cover lid was securelyclosed causing the laser shutter to open. The sample was allowed totemperature stabilize for 5 to 10 minutes. On the menu tools bar,“Auto-Attenuate” was selected to cause the adjustment of laser power tofit the measurement requirements. Once the instrument and sample wasset-up, the scatter intensity graphic display was observed. Patternsshould appear uniform with minimal random spikes due to entrainednano/micro-bubbles or settling large particles.

A measurement was then performed. The developing correlation curve wasalso observed. This curve should display a shape as an “inverted S” andnot “spike” out-of-limits. If the set-up was correct, parameters wereadjusted to collect 100 measurements and “run” was then selected. Theinstrument auto-collected data and discarded correlation curves, notexhibiting Brownian motion behavior. At measurement series completion,retained correlation curves were inspected. All should exhibit expectedshape and displayed between 30% and 90% expected motion behaviors. Atthis point, collected data was saved and software calculated particlesize information. The measurement was repeated to demonstratereproducibility. Resultant graphic displays were then inspected.Residuals should appear randomly dispersed and data measurement pointmust follow calculated theoretical correlation curve. The graphicdistribution display was limited to 0.8 nm to 2 μm. The IntensityDistribution and Mass Distribution histograms were reviewed to findparticle sizes and relative proportions of each, present in thesuspension. All information was then recorded and documented.

FIG. 57 a corresponds to a representative Viscotek output for AT097; andFIG. 57 b corresponds to a representative Viscotek output for AT080. Thenumbers reported in FIGS. 57 a and 57 b correspond to the radii ofparticles detected in each solution. It should be noted that multiple(e.g., hundreds) of data-points were examined to give the numbersreported in Table 12i, and FIGS. 57 a and 57 b are just a selection fromthose measured values.

In an effort to understand further the particles produced as a functionof the different electrode combinations set forth in the Example 7, SEMphotomicrographs of similar magnification were taken of each driedsolution corresponding to each of the eight solutions made in thisExample. These SEM photomicrographs are shown in FIGS. 58 a-58 g. FIG.58 a corresponds to a sample from Run ID AT086 and FIG. 58 g correspondsto a sample from Run ID AT080. Each SEM photomicrograph shows a “1μ”(i.e., 1 micron) bar. The general observable trend from thesephotomicrographs is that particle sizes gradually increase from samplesAT086 through AT083, but thereafter start to increase rapidly withinsamples from AT082-AT080. It should be noted that the particulate matterwas so small and of such low concentration that no images are availablefor Run ID AT097.

It should be noted that samples were prepared for the SEM by allowing asmall amount of each solution produced to air dry on a glass slide.Accordingly, it is possible that some crystal growth may have occurredduring drying. However, the amount of “growth” shown in each of samplesAT082-AT080 is more than could possibly have occurred during dryingalone. It is clear from the SEM photomicrographs that cubic-shapedcrystals are evident in AT082, AT081 and AT080. In fact, nearly perfectcubic-shaped crystals are shown in FIG. 58 g, associated with sampleAT080.

Accordingly, without wishing to be bound by any particular theory orexplanation, when comparing the results of Example 7 with Example 6, itbecomes clear that the creation of the plasma 4 has a profound impact onthis inventive process. Moreover, once the plasma 4 is established,conditions favor the production of metallic-based constituents,including silver-based nanoparticles, including the apparent growth ofparticles as a function of each new electrode set 5, 5′ providedsequentially along the trough member 30. However, if the goal of theprocess is to maintain the suspension of metallic-based nanoparticles insolution, then, under the process conditions of this Example 7, some ofthe particles produced begin to settle out near the last three ElectrodeSets (i.e., Run Id's AT082, AT081 and AT080). However, if the goal ofthe process is to achieve particulate matter settling, then that goalcan be achieved by following the configurations in Runs AT082, AT081 andAT080.

UV-Vis spectra were obtained for each of the settled mixturesAT097-AT080. Specifically, UV-Vis spectra were obtained as discussedabove herein (see the discussion in the section entitled,“Characterization of Materials of Examples 1-5 and Mixtures Thereof”).FIG. 59 a shows the UV-Vis Spectra for each of samples AT097-AT080 forthe wavelengths between 200 nm-220 nm. The spectra corresponding toAT097 is off the chart for this scale, so the expanded view in FIG. 59 bhas been provided. It is interesting to note that for each set ofelectrodes 5, 5′ that are sequentially added along the trough member 30,the spectra associated with AT097 diminishes in amount.

UV-Vis spectra for these same eight samples are also shown in FIG. 59 c.Specifically, this FIG. 59 c examines wavelengths in the 220 nm-620 nmrange. Interestingly, the three samples corresponding to AT080, AT081and AT082, are all significantly above the other five spectra.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), each of the eightsolutions made according to this Example 7 were all diluted to the exactsame ppm for silver in order to compare their relative efficacies in anormalized approach. In this regard, the normalization procedure was,for each of the samples, based on the ppm measurements taken after tendays of settling. Accordingly, for example, samples made according toRun AT080 were diluted from 31.6 ppm down to 4 ppm; whereas the samplesassociated with Run AT083 were diluted from 28.1 ppm, down to 4 ppm.These samples were then further diluted to permit Bioscreen measurementsto be performed, as discussed above herein.

FIG. 60 corresponds to a Bioscreen C Microbiology Reader Run that wasperformed with the same ppm's of silver taken from each of samplesAT097-AT080. The results in FIG. 60 are striking in that the efficacy ofeach of the eight solutions line up perfectly in sequence with thehighest efficacy being AT086 and the lowest efficacy being AT080. Itshould be noted that efficacy for sample AT097 was inadvertently notincluded in this particular Bioscreen run. Further, while results withinany Bioscreen run are very reliable for comparison purposes, resultsbetween Bioscreen runs performed at separate times may not providereliable comparisons due to, for example, the initial bacteriaconcentrations being slightly different, the growth stage of thebacteria being slightly different, etc. Accordingly, no comparisons havebeen made in any of the Examples herein between Bioscreen runs performedat different times.

Example 8 Manufacturing Silver-BASED Nanoparticles/NanoparticleSolutions AT089, AT090 and AT091 Using One or Two Plasmas

This Example utilizes the same basic apparatus used to make thesolutions of Examples 1-5, however, this Example uses only a singleplasma 4 to make AT090 (i.e., similar to AT080); two plasmas 4 to makeAT091 (i.e., similar to AT031); and two plasmas 4 to make AT089 (firsttime run), wherein Electrode Set #1 and Electrode Set #8 both utilizeplasmas 4. This Example also utilizes 99.95% pure silver electrodes foreach of electrodes 1 and 5 in each Electrode Set.

Tables 13a, 13b and 13c summarize portions of electrode design,configuration, location and operating voltages. As shown in Tables13a-13c, the target voltages were on average highest associated withAT089 and lowest associated with AT091.

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 61 a, 61 b and 61 c.Accordingly, the data contained in Tables 13a-13c, as well as FIGS. 61a, 61 b and 61 c, give a complete understanding of the electrode designin each electrode set as well as the target and actual voltages appliedto each electrode for the manufacturing processes.

TABLE 13a Run ID: AT090 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.03 0.22/5.59 2.09 5a 1.62 N/A 1.69 8/203.2 2 5b0.87 N/A 0.94 5b′ 1.08 N/A 1.11 8/203.2 3 5c 1.04 N/A 1.10 5c′ 0.94 N/A0.97 8/203.2 4 5d 1.23 N/A 1.26 5d′ 1.24 N/A 1.30 9/228.6 5 5e 1.42 N/A1.47 5e′ 1.11 N/A 1.12 8/203.2 6 5f 1.03 N/A 1.01 5f′ 1.01 N/A 1.038/203.2 7 5g 1.15 N/A 1.13 5g′ 0.94 N/A 1.02 8/203.2 8 5h 0.81 N/A 1.045h′ 1.03 N/A 1.14  8/203.2** Output Water Temperature 85 C. *Distancefrom water inlet to center of first electrode set **Distance from centerof last electrode set to water outlet

TABLE 13b Run ID: AT091 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.04 0.22/5.59 2.04 5a 1.67 N/A 1.66 8/203.2 2 5b0.94 N/A 0.93 5b′ 1.11 N/A 1.10 8/203.2 3 5c 1.01 N/A 0.98 5c′ 1.07 N/A1.05 8/203.2 4 1d 1.44 0.19/4.83 1.41 5d 1.12 N/A 1.11 9/228.6 5 5e 1.09N/A 1.07 5e′ 0.56 N/A 0.55 8/203.2 6 5f 0.72 N/A 0.71 5f′ 0.72 N/A 0.708/203.2 7 5g 0.79 N/A 0.81 5g′ 0.73 N/A 0.68 8/203.2 8 5h 0.64 N/A 0.685h′ 0.92 N/A 0.89  8/203.2** Output Water Temperature 73 C. *Distancefrom water inlet to center of first electrode set **Distance from centerof last electrode set to water outlet

TABLE 13c Run ID: AT089 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.18 0.22/5.59 2.16 5a 1.80 N/A 1.77 8/203.2 2 5b0.99 N/A 0.99 5b′ 1.15 N/A 1.13 8/203.2 3 5c 1.12 N/A 1.14 5c′ 1.00 N/A0.98 8/203.2 4 5d 1.33 N/A 1.27 5d′ 1.35 N/A 1.32 9/228.6 5 5e 1.51 N/A1.49 5e′ 1.16 N/A 1.12 8/203.2 6 5f 1.05 N/A 1.00 5f′ 1.04 N/A 1.018/203.2 7 5g 1.15 N/A 1.11 5g′ 1.14 N/A 1.10 8/203.2 8 1h 1.23 0.19/4.831.19 5h 1.31 N/A 1.27  8/203.2** Output Water Temperature 78 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 13dshows the results. Note that Table 13d includes a column entitled“Electrode Configuration”. This column contains characters of “1” and“0”. The “1's” represent an electrode configuration corresponding toElectrode Set #1 (i.e., a 1, 5 combination). The “0's” represent anelectrode combination of 5, 5′. Thus, for example, “AT089” isrepresented by “10000001” which means an eight electrode set combinationwas used to make “AT089” and the combination corresponded to Set #1=1,5; Sets #2-#7=5, 5; and Set #8=1, 5.

TABLE 13d Electrode Measured Ag Measured Ag Run ID Configuration PPM(initial) PPM (20 hours) AT089 10000001 44.3 45.0 AT090 10000000 40.837.2 AT091 10010000 43.6 44.3

Table 13d includes a column entitled “Measured Ag PPM (initial)”. Thiscolumn corresponds to the silver content of each of the eight solutionsmeasured within one hour of its production. As shown, the measured ppmfor each of the three Runs were generally similar. However, anothercolumn entitled, “Measured Ag PPM (20 hours)” shows that the “initial”and “20 hours” PPM measurements are essentially the same (e.g., withinoperation error of the AAS) for samples corresponding to Run Id's AT089and AT091. This means that essentially no significant settling of theconstituent particles found in these runs occurred. However, the sampleassociated with Run ID AT090 was examined after 20 hours, a significantportion of the constituent particles had settled, with the samples takenfrom Run AT089 losing about 3.6 ppm out of 40 ppm due to particulatesettling.

As discussed in Example 7, a dynamic light scattering (DLS) approach wasutilized to obtain average particle size made in each of these threesamples. The largest particles were made in AT090; and the smallestparticles were made in AT091. Specifically, FIG. 62 a corresponds toAT090; FIG. 62 b corresponds to AT091; and FIG. 62 c corresponds toAT089.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), each of the threesolutions made according to this Example 8 were all diluted to the exactsame ppm for silver in order to compare their relative efficacies in anormalized manner. In this regard, the normalization procedure was, foreach of the samples, based on the ppm measurement taken after twentyhours of settling. Accordingly, for example, samples made according toRun AT090 were diluted from 37.2 ppm down to 4 ppm; whereas the samplesassociated with Run AT091 were diluted from 44.0 ppm, down to 4 ppm.These samples were then further diluted to permit Bioscreen measurementsto be performed, as discussed above herein. FIG. 63 corresponds to aBioscreen C Microbiology Reader Run that was performed with the sameppm's of silver taken from each of samples AT089-AT091. The results inFIG. 63 show that the efficacy of each of the three solutions line upcorresponding to the particle sizes shown in FIGS. 62 a-62 c, with thehighest efficacy being AT091 and the lowest efficacy being AT090.Further, while results within any Bioscreen run are very reliable forcomparison purposes, results between Bioscreen runs performed atseparate times may not provide reliable comparisons due to, for example,the initial bacteria concentrations being slightly different, the growthstage of the bacteria being slightly different, etc. Accordingly, nocomparisons have been made herein between Bioscreen runs performed atdifferent times.

Example 9 Manufacturing Silver-BASED Nanoparticles/NanoparticleSolutions AT091, AT092, AT093, AT094 and AT095 Using Plasmas in MultipleAtmospheres

This Example utilizes essentially the same basic apparatus used to makethe solutions of Examples 1-5, however, this Example uses two plasmas 4occurring in a controlled atmosphere environment. Controlled atmosphereswere obtained by using the embodiment shown in FIG. 28 h. Specifically,for Electrode Set #1 and Electrode Set #4, this Example uses a “1, 5”electrode configuration wherein the electrode 1 creates a plasma in eachof the following atmospheres: air, nitrogen, reducing, ozone and helium.All other Electrode Sets #2, #3 and #5-#8, have a “5, 5′” electrodeconfiguration. This Example also utilizes 99.95% pure silver electrodesfor each of electrodes 1 and 5 in each Electrode Set.

Tables 14a-14e summarize portions of electrode design, configuration,location and operating voltages. As shown in Tables 14a-14e, the targetvoltages were set to a low of about 400-500 volts (reducing atmosphereand ozone) and a high of about 3,000 volts (helium atmosphere).

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 64 a-64 e. Accordingly, thedata contained in Tables 14a-14e, as well as FIGS. 64 a-64 e, give acomplete understanding of the electrode design in each electrode set aswell as the target and actual voltages applied to each electrode for themanufacturing processes. The atmospheres used for each plasma 4 for eachelectrode 1 for Electrode Set #1 and Electrode Set #4 were as follows:AT091—Air; AT092—Nitrogen; AT093—Reducing or Air-Deprived; AT094—Ozone;and AT095—Helium. The atmospheres for each of Runs AT092-AT095 wereachieved by utilizing the atmosphere control device 35 shown, forexample, in FIG. 28 h. Specifically, a nitrogen atmosphere was achievedaround each electrode 1, 5 in Electrode Set #1 and Electrode Set #4 byflowing nitrogen gas (high purity) through tubing 286 into the inletportion 37 of the atmosphere control device 35 shown in FIG. 28 h. Theflow rate of nitrogen gas was sufficient so as to achieve positivepressure of nitrogen gas by causing the nitrogen gas to create apositive pressure on the water 3 within the atmosphere control device35.

Likewise, the atmosphere of ozone (AT094) was achieved by creating apositive pressure of ozone created by an ozone generator and inputtedinto the atmosphere control device 35, as discussed above herein. Itshould be noted that significant nitrogen content was probably presentin the supplied ozone.

Further, the atmosphere of helium (AT095) was achieved by creating apositive pressure of helium inputted into the atmosphere control device35, as discussed above herein.

The atmosphere of air was achieved without using the atmosphere controldevice 35.

The reducing atmosphere (or air-deprived atmosphere) was achieved byproviding the atmosphere control device 35 around each electrode 1, 5 inElectrode Sets #1 and #4 and not providing any gas into the inletportion 37 of the atmosphere control devices 35. In this instance, theexternal atmosphere (i.e., an air atmosphere) was found to enter intothe atmosphere control device 35 through the hole 37 and the plasma 4created was notably much more orange in color relative to the airatmosphere plasma.

In an effort to understand the composition of each of the plasmas 4, a“Photon Control Silicon CCD Spectrometer, SPM-002-E” (from Blue HillOptical Technologies, Westwood, Mass.) was used to collect the spectrafor each of the plasmas 4.

Specifically, in reference to FIGS. 65 a and 65 b, the Photon ControlSilicon CCD Spectrometer 500, was used to collect spectra (200-1090 nm,0.8/2.0 nm center/edge resolution) on each plasma 4 generated betweenthe electrode 1 and the surface 2 of the water 3. The Spectrometer 500was linked via a USB cable to a computer (not shown) loaded with PhotonControl Spectrometer software, revision 2.2.3. A 200 μm core opticalfiber patch cable 502 (SMA-905, Blue Hill Optical Technologies) wasmounted on the end of a Plexiglas support 503. A laser pointer 501(Radio Shack Ultra Slim Laser Pointer, #63-1063) was mounted on theopposite side 506 of the plexiglas support. This assembly 503 wascreated so that the optical cable 502 could be accurately and repeatedlypositioned so that it was directly aimed toward the same middle portionof each plasma 4 formed by using the laser pointer 501 as an aimingdevice.

Prior to the collection of any spectra created by each plasma 4, theatmosphere control device 35 was saturated with each gas for 30 secondsand a background spectrum was collected with 2 second exposure set inthe software package. The plasma 4 was active for 10 minutes prior toany data collection. The primary spot from the laser 501 was alignedwith the same point each time. Three separate spectra were collected foreach run and then averaged. The results of each spectra are shown inFIGS. 66 a-66 e (discussed later herein in this Example).

TABLE 14a Run ID: AT091 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Air Target Average Voltage Distance Distance Voltage Set #Electrode # (kV) “c-c” in/mm “x” in/mm (kV)  7/177.8* 1 1a 2.040.22/5.59 2.04 5a 1.67 N/A 1.66 8/203.2 2 5b 0.94 N/A 0.93 5b′ 1.11 N/A1.10 8/203.2 3 5c 1.01 N/A 0.98 5c′ 1.07 N/A 1.05 8/203.2 4 1d 1.440.19/4.83 1.41 5d 1.12 N/A 1.11 9/228.6 5 5e 1.09 N/A 1.07 5e′ 0.56 N/A0.55 8/203.2 6 5f 0.72 N/A 0.71 5f′ 0.72 N/A 0.70 8/203.2 7 5g 0.79 N/A0.81 5g′ 0.73 N/A 0.68 8/203.2 8 5h 0.64 N/A 0.68 5h′ 0.92 N/A 0.89 8/203.2** Output Water Temperature 73 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 14b Run ID: AT092 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Nitrogen Target Average Voltage Distance Distance Voltage Set #Electrode # (kV) “c-c” in/mm “x” in/mm (kV)  7/177.8* 1 1a 2.390.22/5.59 2.27 5a 2.02 N/A 1.99 8/203.2 2 5b 1.39 N/A 1.30 5b′ 1.51 N/A1.54 8/203.2 3 5c 1.49 N/A 1.47 5c′ 1.50 N/A 1.52 8/203.2 4 1d 1.640.19/4.83 1.66 5d 1.33 N/A 1.31 9/228.6 5 5e 1.46 N/A 1.47 5e′ 1.05 N/A0.98 8/203.2 6 5f 1.18 N/A 1.13 5f′ 1.13 N/A 1.11 8/203.2 7 5g 1.26 N/A1.20 5g′ 1.17 N/A 1.03 8/203.2 8 5h 0.94 N/A 0.87 5h′ 1.12 N/A 1.07 8/203.2** Output Water Temperature 88 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 14c Run ID: AT093 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Reducing or Air-Deprived Target Average Voltage DistanceDistance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm (kV) 7/177.8* 1 1a 2.04 0.22/5.59 2.02 5a 1.50 N/A 1.49 8/203.2 2 5b 0.76N/A 0.76 5b′ 1.02 N/A 1.03 8/203.2 3 5c 0.91 N/A 0.91 5c′ 0.98 N/A 0.998/203.2 4 1d 1.38 0.19/4.83 1.39 5d 1.01 N/A 0.99 9/228.6 5 5e 0.94 N/A0.92 5e′ 0.39 N/A 0.38 8/203.2 6 5f 0.60 N/A 0.58 5f′ 0.50 N/A 0.488/203.2 7 5g 0.68 N/A 0.65 5g′ 0.55 N/A 0.56 8/203.2 8 5h 0.59 N/A 0.595h′ 0.89 N/A 0.87  8/203.2** Output Water Temperature 75 C. *Distancefrom water inlet to center of first electrode set **Distance from centerof last electrode set to water outlet

TABLE 14d Run ID: AT094 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Ozone Target Average Voltage Distance Distance Voltage Set #Electrode # (kV) “c-c” in/mm “x” in/mm (kV)  7/177.8* 1 1a 2.240.22/5.59 2.20 5a 1.73 N/A 1.74 8/203.2 2 5b 0.93 N/A 0.95 5b′ 1.16 N/A1.18 8/203.2 3 5c 1.09 N/A 1.10 5c′ 1.15 N/A 1.17 8/203.2 4 1d 1.450.19/4.83 1.47 5d 1.08 N/A 1.10 9/228.6 5 5e 0.99 N/A 1.00 5e′ 0.43 N/A0.45 8/203.2 6 5f 0.64 N/A 0.63 5f′ 0.52 N/A 0.56 8/203.2 7 5g 0.71 N/A0.74 5g′ 0.63 N/A 0.64 8/203.2 8 5h 0.66 N/A 0.67 5h′ 0.95 N/A 0.95 8/203.2** Output Water Temperature 76 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 14e Run ID: AT095 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Helium Target Average Voltage Distance Distance Voltage Set #Electrode # (kV) “c-c” in/mm “x” in/mm (kV)  7/177.8* 1 1a 3.090.22/5.59 3.11 5a 2.98 N/A 2.96 8/203.2 2 5b 2.81 N/A 2.80 5b′ 2.86 N/A2.83 8/203.2 3 5c 2.38 N/A 2.38 5c′ 2.32 N/A 2.30 8/203.2 4 1d 2.640.19/4.83 2.58 5d 2.50 N/A 2.49 9/228.6 5 5e 2.06 N/A 2.07 5e′ 1.64 N/A1.63 8/203.2 6 5f 1.34 N/A 1.36 5f′ 1.31 N/A 1.31 8/203.2 7 5g 1.27 N/A1.28 5g′ 1.12 N/A 1.12 8/203.2 8 5h 1.08 N/A 1.08 5h′ 1.26 N/A 1.25 8/203.2** Output Water Temperature 95 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 14fshows the results. Note that Table 14f includes a column entitled“Electrode Configuration”. This column contains characters “1” and “0”.The “1's” represent an electrode configuration corresponding toElectrode Set #1 (i.e., a 1, 5 combination). The “0's” represent anelectrode combination of 5, 5′. Thus, for example, “AT091” isrepresented by “10010000” which means an eight electrode set combinationwas used to make “AT091” and the combination corresponded to Set #1=1,5; Set #2=5, 5; Set #3=5, 5; Set #4=1, 5 and Set #5-Set #8=5, 5.

TABLE 14f Electrode Measured Ag Run ID Configuration PPM AtmosphereAT091 10010000 44.0 Air AT092 10010000 40.3 Nitrogen AT093 10010000 46.8Reducing AT094 10010000 44.5 Ozone AT095 10010000 28.3 Helium

Table 14f includes a column entitled “Measured Ag PPM”. This columncorresponds to the silver content of each of the eight solutions. Asshown, the measured ppm produced in each of the atmospheres of air,nitrogen, reducing and ozone were substantially similar. However, theatmosphere of helium (i.e., AT095) produced a much lower ppm level.Also, the size of particulate matter in the AT095 solution wassignificantly larger than the size of the particulate matter in each ofthe other four solutions. The particulate sizes were determined bydynamic light scattering methods, as discussed above herein.

It is clear from FIGS. 66 a-66 e that each spectra shown therein createdfrom the plasma 4 had a number of very prominent peaks. For example,those prominent peaks associated with each of the atmospheres of air,nitrogen, reducing and ozone all have strong similarities. However, thespectral peaks associated with the spectra creating by the plasma 4(i.e., when helium was provided as the atmosphere) are quite differentfrom the other four peaks. In this regard, FIG. 66 a shows the completespectral response for each plasma 4 for each of the gasses used in thisExample over the entire wavelength range of 200-1000 nm. FIGS. 66 b and66 c focus on certain portions of the spectra of interest and identifyby name the atmospheres associated with each spectrum. FIGS. 66 d and 66e identify specific common peaks in each of these spectra. Specifically,FIGS. 67 a-67 f are excerpted from the articles discussed above herein.Those FIGS. 67 a-67 f assist in identifying the active peaks in theplasma 4 of this Example 9. It is clear that spectral peaks associatedwith the helium atmosphere are quite different from spectral peaksassociated with the other four atmospheres.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), each of the five solutionsmade according to this Example 9 were all diluted to the exact same ppmfor silver in order to compare their relative efficacies in a normalizedmanner. Accordingly, for example, samples made according to Run AT091were diluted from 44.0 ppm down to 4 ppm; whereas the samples associatedwith Run AT095 were diluted from 28.3 ppm, down to 4 ppm. These sampleswere then further diluted to permit Bioscreen measurements to beperformed, as discussed above herein. FIG. 68 corresponds to a BioscreenC Microbiology Reader Run that was performed with the same ppm's ofsilver taken from each of samples AT091-AT095. The results in FIG. 68show the highest efficacy being AT094 and AT096 (note: AT096 was madeaccording to Example 10, and shall be discussed in greater detailtherein) and the lowest efficacy being AT095. Further, while resultswithin any Bioscreen run are very reliable for comparison purposes,results between Bioscreen runs performed at separate times may notprovide reliable comparisons due to, for example, the initial bacteriaconcentrations being slightly different, the growth stage of thebacteria being slightly different, etc. Accordingly, no comparisons havebeen made herein between Bioscreen runs performed at different times.

Example 10 Manufacturing Silver-BASED Nanoparticles/NanoparticleSolution AT096, Using a Diode Bridge to Rectify an AC Power Source toForm Plasmas

This Example utilizes essentially the same basic apparatus used to makethe solutions of Examples 1-5, however, this Example uses two plasmas 4formed by a DC-like Power Source (i.e., a diode bridge-rectified powersource). Specifically, for Electrode Set #1 and Electrode Set #4, thisExample uses a “1, 5” electrode configuration wherein the electrode 1creates a plasma 4 in accordance with the power source shown in FIG. 32c. All other Electrode Sets #2, #3 and #5-#8, had a “5, 5′” electrodeconfiguration. This Example also utilizes 99.95% pure silver electrodesfor each of electrodes 1 and 5 in each Electrode. Set.

Table 15 summarizes portions of electrode design, configuration,location and operating voltages. As shown in Table 15, the targetvoltages were set to a low of about 400 volts (Electrode Set #4) and ahigh of about 1,300 volts (Electrode Set #3).

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIG. 69. Accordingly, the datacontained in Table 15, as well as FIG. 69, give a complete understandingof the electrode design in each electrode set as well as the target andactual voltages applied to each electrode for the manufacturingprocesses.

TABLE 15 Run ID: AT096 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 0.76 0.19/4.83 0.69 5a 0.68 N/A 0.68 8/203.2 2 5b1.25 N/A 1.22 5b′ 1.13 N/A 1.11 8/203.2 3 5c 1.18 N/A 1.15 5c′ 1.28 N/A1.27 8/203.2 4 1d 0.41 0.19/4.83 0.47 5d 0.64 N/A 0.63 9/228.6 5 5e 1.02N/A 0.99 5e′ 0.93 N/A 0.91 8/203.2 6 5f 0.76 N/A 0.74 5f′ 0.76 N/A 0.768/203.2 7 5g 0.91 N/A 0.90 5g′ 0.80 N/A 0.79 8/203.2 8 5h 0.75 N/A 0.745h′ 0.93 N/A 0.93  8/203.2** Output Water Temperature 80 C. *Distancefrom water inlet to center of first electrode set **Distance from centerof last electrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 15ashows the results. Note that Table 15a includes a column entitled“Electrode Configuration”. This column contains characters “1*” and “0”.The “1*” represents an electrode configuration corresponding toElectrode Set #1 (i.e., a 1, 5 combination, wherein the electrode 1 isnegatively biased and the electrode 5 is positively biased. The “0's”represent an electrode combination of 5, 5′.

TABLE 15a Electrode Measured Ag Run ID Configuration PPM AtmosphereAT096 1*001*0000 51.2 Air

Table 15a includes a column entitled “Measured Ag PPM”. This columncorresponds to the silver content of the solution. As shown, themeasured ppm was 51.2 ppm, which was substantially higher than any othersamples made by the other eight electrode sets utilized in any otherExample.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), this solution AT096 wastested against each of the five solutions made according to Example 9above herein. Specifically, all of the five solutions from Example 9 andAT096 were diluted to the exact same ppm for silver in order to comparetheir relative efficacies in a normalized manner as discussed in Example9. FIG. 68 corresponds to a Bioscreen C Microbiology Reader Run that wasperformed with the same ppm's of silver taken from each of samplesAT092-AT096. The results in FIG. 68 show that AT096 was among the bestperforming solutions. Further, while results within any Bioscreen runare very reliable for comparison purposes, results between Bioscreenruns performed at separate times may not provide reliable comparisonsdue to, for example, the initial bacteria concentrations being slightlydifferent, the growth stage of the bacteria being slightly different,etc. Accordingly, no comparisons have been made herein between Bioscreenruns performed at different times.

The atmosphere used for AT096 was air, and the corresponding spectra ofthe air plasma is shown in FIGS. 70 a, 70 b and 70 c. These spectra aresimilar to those set forth in FIGS. 66 a, 66 b and 66 c. Additionally,FIGS. 70 a, 70 b and 70 c show spectra associated with the atmospheresof nitrogen, reducing or air-deprived and helium, all produced accordingto the set-up conforming to that used to make the plasma 4 in AT096.These atmospheres and the measurements associated therewith, were madein accordance with the teachings in Example 9.

Similarly, FIGS. 71 a, 71 b and 71 c show a similar set of spectra takenfrom plasmas 4 when the polarity of the electrode 1 used earlier in thisExample has been reversed. In this regard, all of the atmospheres forair, nitrogen, reducing or air-deprived, ozone and helium are alsoutilized but in this case the electrode 1 has become positively biasedand the electrode 5 (i.e., the surface 2 of the water 3) has becomenegatively biased.

Example 11 Efficacy and Cytotoxicity Testing of Related NanoparticleSolutions

This Example follows the teachings of Examples 2 [AT060], 3[AT031-AT064] and 4 [BT006-BT012] to manufacture two differentsilver-based nanoparticle/nanoparticle solutions and one zinc-basednanoparticle/nanoparticle solution. Additionally, a new and differentsolution (i.e., PT001) based in part on the inventive process for makingBT006 and BT012 was also produced. Once produced, three solutions weretested for efficacy and cytotoxicity.

Specifically, the solution made by the method of Example 2 (i.e., AT060)was tested for cytotoxicity against Murine Liver Epithelial Cells, asdiscussed above herein. The results are shown in FIG. 72 a. Likewise, asolution produced according to Example 3 (i.e., AT031) was made “AT064”and was also likewise tested for cytotoxicity. The results are shown inFIG. 72 b. Further, material produced according to Example 4 (i.e.,BT006) was made and designated “BT012” and was likewise tested forcytotoxicity. The results are shown in FIG. 72 c.

Mixtures of the materials (i.e., AT060, AT064 and BT012) were then madein order to form GR5 and GR8, in accordance with what is shown in Table8 herein relating to the solutions GR5 and GR8. Specifically, AT064 andBT012 were mixed together to form GR5; and AT060 and BT012 were mixedtogether to form GR8 to result in the amounts of silver and zinc in eachbeing the same as what is shown in Table 8.

Once the solutions of GR5 and GR8 were formed, the cytotoxicity for eachwas measured. Specifically, as shown in FIG. 73 a and FIG. 73 b thecytotocicity of GR5 was determined. In this regard, the LD₅₀ for GR5,based on silver nanoparticle concentration, was 5.092; whereas the LD₅₀based on total nanoparticle concentration (i.e., both silver and zinc)was 15.44.

In comparison, FIG. 74 a shows the LD₅₀, based on silver nanoparticleconcentration, for GR8, which was 4.874. Similarly, FIG. 74 b shows theLD₅₀ equal to 18.05 regarding the total nanoparticle concentration(i.e., total of silver and zinc particles) in GR8.

The other inventive material in this Example 11, “PT001”, was made bythe following process. Electrode Set #1 was a 1, 5 combination.Electrode Set#2 was also a 1, 5 combination. There were no electrodesets at positions 2-8. Accordingly, the designation for this electrodecombination was a “11XXXXXX”. The composition of each of electrodes 1and 5 in both Electrode Sets #1 and #2 were high-purity platinum (i.e.,99.999%). Table 16a sets forth the specific run conditions for PT001.

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIG. 75. Accordingly, the datacontained in Table 16a, as well as in FIG. 75, give a completeunderstanding of the electrode design in each electrode set as well asthe target and actual voltages applied to each electrode for themanufacturing processes.

TABLE 16a Run ID: PT001 Flow Rate: 150 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 1.90 .22/5.59 2.00 5a 1.37 N/A 1.51 8/203.2 2 1b0.78 .22/5.59 0.87 5b 0.19 N/A 0.18  57/1447.8** N/A N/A N/A N/A N/A N/AOutput Water Temperature 49 C. *Distance from water inlet to center offirst electrode set **Distance from center of last electrode set towater outlet

The solution PT001 was then treated as if it had an equivalent volume ofzinc-based nanoparticles equivalent to those present in BT012 (i.e., 23ppm zinc). In other words, a volume of about 150 ml of PT001 was addedto about 50 ml of AT064 to produce GR5* and a volume of about 170 ml ofPT001 was added to about 33 ml of AT060 to produce GR8*. Once mixed,these new material solutions (i.e., GR5* and GR8*) were allowed to sitfor 24 hours prior to being tested for cytotoxicity.

FIG. 76 a shows that the LD₅₀ for GR5* was 8.794 (i.e., based on totalsilver nanoparticle concentration). This compares with an LD₅₀ forsilver alone in AT064 of 7.050; and an LD₅₀ for GR5 (based on silverconcentration alone) of 5.092.

Likewise, FIG. 76 b shows the cytotoxicity of GR8* as a function ofsilver nanoparticle concentration. The LD₅₀ (i.e., based on silvernanoparticle concentration) for GR8* is 7.165. This compares directly toan LD₅₀ for AT060 of 9.610 and an LD₅₀ for GR8 (based on silverconcentration alone) of 4.874.

Accordingly, the LD₅₀ of each of GR5* and GR8* was higher than thecorresponding LD₅₀'s of GR5 and GR8, respectively (i.e., with regard tothe silver content in each of the mixes GR5 and GR8).

The biological efficacies against E. coli of each of GR5 and GR5* werethen compared. Specifically, FIG. 77 a shows a Bioscreen reaction, runaccording to the procedures discussed above herein. In this Bioscreenreaction, it is clear that the performance of GR5 and GR5* weresubstantially identical.

Likewise, a comparison between the biological efficacy against E. coliwas also performed for GR8 and GR8*. This comparison is shown in FIG. 77b. GR8 and GR8* both had substantially identical biological performance.

Accordingly, this Example shows that cytotoxicity of solutions GR5 andGR8 can be lowered by utilizing the solution PT001 instead of BT012 ineach of the mixes GR5 and GR8. Moreover, such cytotoxicity is loweredwithout sacrificing biological efficacy against E. coli, as shown inFIGS. 77 a and 77 b.

However, it should be understood that other in vivo benefits can beobtained by the presence of, for example, the material corresponding toBT012 in the solutions GR5 and GR8.

Example 12 Comparison of Biological Performance of Two DifferentSilver-Based Nanoparticles/Nanoparticle Solutions by Adding VariableZinc Nanoparticles/Nanoparticle Solutions and Related Aging Study

The materials disclosed in Example 11, namely AT064 and AT060 and anequivalent to BT012 (i.e., BT013) were mixed together in varyingproportions to determine if any differences in biological efficacy couldbe observed (e.g., similar to the studies shown in FIGS. 49 and 50).However, in this study, biological efficacy as a function of timeelapsed between mixing the solutions together and testing for biologicalefficacy was investigated.

Specifically, FIG. 78 a shows biological efficacy results of a varietyof mixtures of AT064 with BT013 wherein the amount of AT064 remains at aconstant ppm relative to the amount of BT013 added. Accordingly, thisresulted in an increasing sequence of zinc being added as follows 2 ppmZn, 4 ppm Zn, 8 ppm Zn and 13 ppm Zn. These differing amounts of Znadditions were achieved by a similar approach used for generating thedata associated with FIGS. 49 and 50. FIG. 78 a clearly shows that thebiological performance of AT064 was enhanced by adding BT013. Note thatefficacy tests were begun immediately after mixing AT064 and BT013together. Specifically, FIG. 78 a shows biological performance of thevarious silver-zinc mixtures wherein such mixtures were mixed as closein time as possible (Δt=0) to beginning the Bioscreen run. The 13 ppm Znadded showed great enhanced performance relative to AT064 as well as theother lower ppm zinc levels. However, only slight differences inperformance existed between 2 ppm, 4 ppm and 8 ppm Zn additions,relative to each other. These relative performances were greatlyenhanced in FIG. 78 b.

Specifically, FIG. 78 b shows a Δt=1, which corresponds to allowing theraw materials AT064 and BT013 to sit undisturbed after being mixedtogether for approximately 24 hours prior to being placed in theBioscreen test. Clear distinctions in biological efficacy are seenbetween all of the Zn ppm additions to AT064, with the 13 ppm stillperforming equal to the negative control after 0.8 days. Accordingly,enhanced performance by mixing of BT013 with AT064 was achieved byallowing a period of time to elapse after mixing, prior to biologicalefficacy testing.

FIG. 79 a shows slightly different results from FIG. 78 a. Particularly,FIG. 79 a shows the changes in biological efficacy of AT060 when mixedwith 2 ppm Zn, 4 ppm Zn, 8 ppm Zn and 13 ppm Zn. In contrast to FIG. 78a, the 2 ppm and 4 ppm zinc additions to AT060 did not show any changein biological efficacy after mixing together and conducting immediatebiological testing. Accordingly, with Δt=0 in this experiment, whichcorresponds to mixing AT060 with BT013 and immediately testing in theBioscreen, no enhancement in efficacy was observed for the addition of 2ppm and 4 ppm Zn. Slightly enhanced performance of AT060 was observedwith 8 ppm Zn and 13 ppm Zn.

However, the biological efficacy results are dramatically different inFIG. 79 b. In this efficacy experiment, the components AT060 and BT013were allowed to sit together for Δt=1, which corresponds toapproximately 24 hours. After allowing the materials AT060 and BT013 tosit for approximately 24 hours, and then subsequent Bioscreen testingwas performed, a spread in efficacy, similar to that shown in FIG. 78 b,was observed. Specifically, there are clear biological efficacydistinctions that exist between AT060 with additions of each of 2 ppm, 4ppm, 8 ppm and 13 ppm of Zn added thereto, respectively.

Additional biological efficacy tests were run to determine if additional“hold time” had any further enhancing effects. Specifically, the data inFIG. 79 c correspond to a “hold time” of Δt=2 (i.e., approximately 48hours) prior to testing for efficacy changes of AT060 as a function ofincreasing Zn ppm concentration. It was determined that the efficacychanges shown in FIG. 79 c were substantially identical to the efficacychanges shown in FIG. 79 b. Accordingly, it is clear that reactionswhich occurred in FIG. 79 b did not seem to occur to any greater extentbetween 24 hours and 4.8 hours.

In an effort to clarify the differences in biological efficacy observedin FIG. 78 a vs. FIG. 78 b, and in FIG. 79 a vs. FIGS. 79 b and 79 c, adynamic light scattering (“DLS”) experiment was performed, according tothe procedures discussed above herein.

Specifically, two sets of DLS tests were performed. The first test mixedtogether AT064 and BT013 in proportion to produce GR5 (i.e., about 50 mlof AT064 and about 150 ml of BT013). The second test mixed togetherAT060 and BT013 in proportion to produce GR8 (i.e., about 33 ml of AT060and about 170 ml of BT013).

The results of the DLS measurements as a function of time after mixingthe aforementioned materials together are shown in FIGS. 80 and 81.Specifically, FIGS. 80 a-80 f show DLS size measurements taken at sixdifferent times, namely, t=0; t=80 minutes; t=5 hours; t=5.5 hours; t=6hours; and t=21 hours. Similarly, FIGS. 81 a-81 e show DLS sizemeasurements taken at five different times, namely, t=0; t=80 minutes;t=4 hours; t=5 hours; and t=21 hours.

It is clear from the results shown in FIGS. 80 and 81, that one or morereaction(s) are occurring between AT064 and BT013; as well as one ormore reaction(s) occurring between AT060 and BT013. While the initialparticle sizes of AT064 and AT060 may be different, according to, forexample, the TEM photomicrographs of FIG. 43, discussed earlier herein,the concentration and nature of solutions containing Ag and solutionscontaining Zn are different in each of GR5 and GR8. In any event, DLSmeasurements of both mixtures comprising GR5 and GR8 show relativelylarge particle sizes being present. Perhaps some particle agglomentationmay be occurring. However, after a period of 5-6 hours, DLS measurementsindicate the detected particle sizes have significantly diminished.Further, after 21 hours, the DLS measurements suggest that the detectedparticle sizes were substantially equivalent.

Without wishing to be bound by any particular theory or explanation, itappears that particle size and biological performance (e.g., efficacyagainst E. coli) are related.

The invention claimed is:
 1. A substantially continuous process formodifying at least one liquid comprising: flowing at least one liquidthrough at least one trough member, said at least one liquid having anupper surface and a flow direction; providing at least oneplasma-forming electrode; creating at least one plasma between said atleast one plasma-forming electrode and at least a portion of said uppersurface of said at least one flowing liquid; providing at least one setof metallic-based electrodes in contact with said at least one flowingliquid and located downstream in said flow direction from said at leastone plasma-forming electrode; and conducting at least oneelectrochemical reaction at said at least one set of metallic-basedelectrodes to produce at least some metallic-based constituents withinsaid at least one liquid.
 2. The process of claim 1, wherein said atleast one trough member comprises a conduit with at least one inlet andat least one outlet which permits said at least one liquid to flowtherein.
 3. The process of claim 1, wherein said at least one plasmacomprises an adjustable plasma.
 4. The process of claim 1, wherein saidat least one plasma-forming electrode provides at least one speciestherefrom that is present in said at least one plasma.
 5. The process ofclaim 1 wherein said at least some metallic-based constituents comprisemetallic-based ions.
 6. The process of claim 1 wherein said at leastsome metallic-based constituents comprise metallic-based nanoparticles.7. The process of claim 1, wherein said at least one plasma-formingelectrode comprises a metal.
 8. The process of claim 7, wherein at leastone constituent of said at least one plasma-forming electrode is presentin said plasma.
 9. The process of claim 8, wherein at least a portion ofsaid at least one liquid comprises said at least one constituent aftersaid liquid has flowed past said at least one plasma-forming electrode.10. The process of claim 9, wherein said at least one electrochemicalreaction occurs after said at least one constituent of said at least oneplasma-forming electrode is present in said at least one liquid.
 11. Theprocess of claim 10, wherein at least two metallic-based electrode setscontact said at least one liquid to cause said at least oneelectrochemical reaction to occur.
 12. The process of claim 11, whereinat least one power source is provided between said at least twoelectrode sets to cause said at least one electrochemical reaction tooccur.
 13. The process of claim 11, wherein said at least two electrodesets form said at least some metallic-based constituents in said atleast one liquid.
 14. The process of claim 11, wherein said at least twoelectrode sets comprise at least one metallic constituent.
 15. Theprocess of claim 1, wherein said at least one liquid comprises water.16. The process of claim 1, wherein said at least one plasma-formingelectrode comprises at least one material selected from the groupconsisting of platinum, titanium, zinc, silver, copper, gold, alloys andmixtures thereof.
 17. The process of claim 1, wherein at least twoplasma-forming electrodes are provided.
 18. The process of claim 1,further comprising at least one atmosphere control device providedaround said at least one plasma-forming electrode.
 19. A substantiallycontinuous process for modifying at least one liquid comprising:creating a flow direction of at least one liquid through at least onetrough member; providing at least one plasma-forming electrode spacedapart from a surface of said at least one liquid; forming at least oneplasma between said at least one plasma-forming electrode and saidsurface of said at least one liquid; providing at least one set ofmetallic-based electrodes contacting at least a portion of said at leastone liquid, said at least one set of electrodes contacting said at leastone liquid after said liquid has flowed past said at least oneplasma-forming electrode; and causing said at least one set ofmetallic-based electrodes to react with at least a portion of said atleast one liquid to produce at least some metallic-based constituentswithin said at least one liquid.
 20. The process of claim 19, whereinsaid at least one liquid is pumped through said at least one troughmember, said at least one trough member having an inlet portion and anoutlet portion.
 21. The process of claim 20, wherein at least twoplasma-forming electrodes are located closer to said inlet portion thansaid outlet portion and at least two sets of metallic-based electrodesare located closer to said outlet portion than said inlet portion. 22.The process of claim 21, wherein said flowing liquid contacts said atleast two plasma-forming electrodes prior to contacting said at leasttwo sets of metallic-based electrodes.
 23. The process of claim 19,wherein said at least some metallic-based constituents comprisemetallic-based nanoparticles.
 24. The process of claim 19, wherein saidat least one set of metallic-based electrodes comprises at least onematerial selected from the group consisting of platinum, titanium, zinc,silver, copper, gold, alloys and mixtures thereof.
 25. The process ofclaim 19, wherein said at least one plasma-forming electrode and said atleast one set of metallic-based electrodes comprise predominantlydifferent metals.
 26. The process of claim 19, wherein said at least oneplasma-forming electrode and said at least one set of metallic-basedelectrodes comprise substantially the same metals.
 27. The process ofclaim 19, wherein at least two sets of metallic-based electrodes areprovided.
 28. The process of claim 19, wherein said at least one troughmember comprises at least one of a linear shape, a “Y-shape” and a“Ψ-shape”.
 29. The process of claim 19, further comprising at least onecontrol device for adjusting the location of at least one electroderelative to the surface of the liquid, wherein said at least oneelectrode is selected from the group consisting of said at least oneplasma-forming electrode and said at least one set of metallic-basedelectrodes.
 30. The process of claim 29, wherein said at least onecontrol device maintains a substantially constant voltage across said atleast one electrode by adjusting said location.
 31. The process of claim19, wherein said at least one plasma-forming electrode is locatedupstream from a plurality of sets of metallic-based electrodes.
 32. Theprocess of claim 19, wherein at least two plasma-forming electrodes arelocated upstream from a plurality of sets of metallic-based electrodes.33. The process of claim 31, wherein at least one atmosphere controldevice surrounds said at least one plasma-forming electrode.
 34. Theprocess of claim 19, wherein said at least one liquid comprises water,said at least one plasma-forming electrode comprises at least at leastone material selected from the group consisting of platinum, titanium,zinc, silver, copper, gold, alloys and mixtures thereof, and said atleast one set of metallic-based electrodes comprises at least onematerial selected from the group consisting of platinum, titanium, zinc,silver, copper, gold, alloys and mixtures thereof.
 35. A substantiallycontinuous process for creating at least one metallic constituent inwater comprising: flowing water through at least one trough member, saidwater having an upper surface; contacting at least one plasma with atleast a portion of said upper surface of said water; contacting at leastone set of metallic-based electrodes with said water after said waterhas contacted said at least one plasma and causing at least oneelectrochemical reaction to occur within said water, thereby formingsaid at least one metallic constituent in said water.
 36. The process ofclaim 35, wherein a substantially constant voltage is applied to said atleast one set of metallic-based electrodes.
 37. The process of claim 35,wherein said at least one liquid comprises water, said at least oneplasma-forming electrode comprises at least one material selected fromthe group consisting of platinum, titanium, zinc, silver, copper, gold,alloys and mixtures thereof, and said at least one set of metallic-basedelectrodes comprises at least one material selected from the groupconsisting of platinum, titanium, zinc, copper, gold, alloys andmixtures thereof.
 38. A substantially continuous process for creating atleast one metallic constituent in water comprising: creating a flowdirection of water in at least one trough member, said water having anupper surface; providing at least one plasma-forming electrode spacedapart from said upper surface of said water; forming at least one plasmabetween said at least one plasma-forming electrode and said uppersurface of said water; and contacting at least one set of metallic-basedelectrodes with said water and causing at least one electrochemicalreaction to occur with said at least one set of metallic-basedelectrodes and said water to produce at least some metallic-basednanoparticles within said water.
 39. The process of claim 38, whereinsaid flowing water contacts said at least one plasma prior to contactingsaid at least one set of metallic-based electrodes.
 40. The process ofclaim 38, wherein at least one liquid comprises water, said at least oneplasma-forming electrode comprises at least at least one materialselected from the group consisting of platinum, titanium, zinc, silver,copper, gold, alloys and mixtures thereof, and said at least one set ofmetallic-based electrodes comprises at least one material selected fromthe group consisting of platinum, titanium, zinc, silver, copper, gold,alloys and mixtures thereof.